JPH01238590A - Production organosilicon compound - Google Patents

Abstract

PURPOSE:To inexpensively obtain the title compound useful as a silane coupling agent, silylating agent, etc., by hydrosilylating SiH4 with a hydrocarbon compound containing unsaturated carbon-carbon bond in the presence of a catalyst comprising a specific metallic compound. CONSTITUTION:(A) SiH4 is hydrosilylated with (B) a hydrocarbon compound preferably ethylene, propylene, butene, isobutene, butadiene, styrene, acetylene or propyne) containing carbon-carbon double bond (C=C) and/or carbon-carbon triple bond (CidenticalC) in the presence of a catalyst (preferably platinum, palladium, iron, cobalt, nickel, ruthenium or rhodium) comprising a metal of groups VII, VIA or VIIA of the periodic table or compounds of the metals as a catalytic constituent component at 0-400 deg.C, preferably 50-200 deg.C to give the aimed compound.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a method for producing alkylsilanes or alkenylsilanes by subjecting SiH and an alkene or alkyne compound to a hydrosilylation reaction (addition reaction) in the presence of a catalyst. Regarding.

[Background technology]

Organosilicon compounds are generally a general term for compounds having a 5t-C bond, and the organosilicon chemical industry is currently undergoing rapid development, as typified by silicone (polyorganosiloxane), and methods for producing organosiliconized metals are rapidly changing. There are several known methods, and the following methods are representative.

(1) Si+RCJ! → RzSiCh, R
zSiCl, R31CI3, Si[(,l.

(2) nRMgX +5iC14→R11SiCI
4-, +nMgXC1(3) Na+RC1+Ei
Si-CI −+ 5t-R+ NaCI(4) C
HzSiHClz + RCH=CHz→R-CHzC
HtSi(CHs)Ch(5)○+)Is iC13-
σ5iCI, +H.

(6) <Ward E>-CI + CH ko31) IC1z
→CH Tsu (<E>) st C1 1 1 HCI (1
) is Rocho's direct method, which directly produces organosilicon compounds from metallic silicon and halogenated hydrocarbons, and is a method for producing alkylchlorosilanes, which are the most important basic raw materials in the current organosilicon industry. . As the halogenated hydrocarbon RC2, methyl chloride and chlorobenzene have been industrialized, and other halogenated hydrocarbons have low yields (not industrial).

On the other hand, (2) is a Grignard method, and (3) is a dechlorination reaction using metallic sodium, and although any alkyl group can be introduced, the Grignard reagent and metallic sodium are expensive and are not economical.

Although (4) is a method similar to the present invention, there is a major problem in that the raw materials are limited to HSiCh and C15SiHC1□, which is a by-product of the direct method.

In addition, (5) and (6) are both high-temperature reactions, and the raw materials are O,0OCI, CI! -CHC11H3ICh, and (:HsSiHCl).

As mentioned above, the basic raw materials in the current organosilicon industry are mostly methyl or phenylchlorosilanes.
Using these silicon compounds as starting materials, various functional substances such as silicones, silane coupling agents, and silylating agents have been developed.

However, the problems with conventional organosilicon industrial processes that use chlorosilanes as basic raw materials are: (1) high process corrosion due to the chlorine-based nature, including the generation of hydrogen chloride; (2) high complexity of reaction steps; , (2) Due to raw material constraints, methyl-based materials are mainly used, and at least one of the alkyl groups must contain a methyl group.

The present invention was made to solve these problems, and is an economical and highly functional product using 5in4 as a starting material, which has become industrially produced at low cost with the development of the semiconductor industry in recent years. This provides an excellent new method for producing organic silicon compound raw materials.

Regarding the method of synthesizing alkylsilanes and alkenylsilanes by hydrosilylation reaction (addition reaction) between SiL and alkenes or alkynes, there have been few research examples because 5iHa has been difficult to obtain and expensive. Slightly, Z.

Naturforsch, ), 56444 (195
0); Ibid., 76.207 (1952); Zeitschrift Fair Anorganische Land Allgemeine Hemi (Z, Anorg.

Allgam, Chem, ) 273, 275 (1953
); Journal of American Chemical
Society (J, Am.

Chem, Soc, ) 76.3897 (1954);
According to these reports, there are only a few cases reported in U.S. Pat, 2786862 (1957), etc.
The reaction temperature is as high as 400 to 500°C, and it is a non-catalytic thermal decomposition reaction. In addition, the yield was low, and the selectivity of the silane compound produced was insufficiently controlled.

The present invention focused on Sign as an industrial organosilicon raw material, and made earnest efforts to develop an industrial route for synthesizing organosilicon compounds from 5iHa, and was able to arrive at the present invention.

[Summary of the invention]

That is, the present invention provides 5i)1. and at least one carbon-carbon double bond (C
-C) and/or carbon-carbon triple bond (C; C
) is the first hydrocarbon compound in the periodic table.
Silicon, characterized by carrying out a hydrosilylation reaction in the temperature range of 0 ° C. to 400 ° C. in the presence of a catalyst consisting of a metal of Group VIA, Group VIIA, or a catalyst containing a compound of the metal as a catalyst component. -Carbon bond (Si-C)
More specifically, the organosilicon compound is an alkylsilane represented by the general formula JSiH4-a (where R is a hydrocarbon group and n is 1, 2.3 or 4). This is a method for producing alkenylsilanes or alkenylsilanes.

[Detailed disclosure of the invention]

The present invention will be explained in detail below.

SiH4 used as a raw material in the present invention has been mass-produced as a semiconductor gas due to the remarkable development of the semiconductor industry in recent years, and has recently become available industrially at low cost. Methods for producing SiH4 include, for example, a method in which a magnesium alloy of silicon (MgzSi, etc.) is reacted with an aqueous solution of hydrohalic acid, a method in which silicon tetrachloride is reduced with a reducing agent such as lithium hydride, and a method in which asymmetric trichlorosilane is used. Methods such as chemical reactions are well known, and for example, in the present invention, products produced by any of these methods can be suitably used.

Another raw material is a compound having at least one carbon-to-carbon double bond (C-C) and/or carbon-to-carbon triple bond (CIC) in its molecule, such as an alkene or an alkyne. It can also have a functional group. Specific examples include CHt-CHt, CHz-CH-CHs, C
Hz-CI-CJs -CHz-C(CHi) z,C
Hg=CH-CH-CHz, CHz-CH-CsHt
, CHg=CH-C4H9, CHz-C)l-CsH+
+, CL = C max CHz, CHz-CH-CHz-C
H-CH-CHs, CI(20)l, CH2C-CH
,,CHzIICHCISCL-CH-CHzCl
-CTo-CH-CHz-NHz, CHz=CHCHt
NHCONHz, CHz-CHCHJCO,0CI(
-CTo, HtC-IC-ecH=cHt, 0-C(
CHz)=CHzCHI-C-Ca0co,,DCH
ICI, CH, Wing CHecH寞C1,, CHx-CH-
CHt訃＠CH*-CI =CH(J ICHz CH
J Hz, and the like. Of course, two or more types of these can be used at the same time.

Next, the catalyst used in the present invention is a catalyst consisting of a metal of Group 1, Group VIA, or Group VIIA in the Periodic Table (New Experimental Chemistry Course, published by Maruzen Co., Ltd. (1977)) or a compound of the metal. It is a catalyst containing as a catalyst component, for example, specifically, Fe, CO5Ni, Ru
5Rh, Pd, Os, Ir%Pt, Cr, M
o, -1 Metals such as Mn, Tc, Re;, Fe
(Go)s, Cot(CO)s, LJi (olefin), LtNiClt, RIIClx, L*RhCl,
La1d, LzPdClz.

IrCl3, L4Pt, ((olefin)PtC
h)z, HiPtCli ・6HtO1R4(Co)z
, RuC1t(Pφ,)1, Cr(Co)i, Mn
t(Go)to, (where φ is phenyl and L is PR
metal complexes such as h3 or PH1); Pt/C.

Examples include metals supported on activated carbon such as Pd/C. Catalysts can be homogeneous or heterogeneous, and most of them are commercially available and readily available. Of course, it can also be easily synthesized. In the present invention, the above-mentioned metal or its compound is an essential component of the catalyst, and it is of course possible to include other catalyst components at the same time.

In the present invention, 5i14 and the above-mentioned hydrocarbon are reacted at 0°C to 400''C in the presence of the above-mentioned catalyst.

The reaction is not particularly limited except for the use of the above-mentioned reaction temperature and catalyst, and can be carried out in either a gas phase or a liquid phase.

The reaction temperature ranges from O'C to 400C, preferably from 50C to 200C, and the catalyst may be either homogeneous or heterogeneous.

To give specific examples of reaction methods, for example, when carried out in a gas phase, 5iHa and a hydrocarbon compound such as a gaseous alkene or alkyne are introduced onto the surface of a solid catalyst and reacted, and when carried out in a liquid phase, a method is used in which 5iHa and a hydrocarbon compound such as a gaseous alkene or alkyne are introduced onto the surface of a solid catalyst. Si in a liquid hydrocarbon compound containing
Methods such as blowing H4 can be adopted, and in the latter case, Si such as benzene, heptane, hexane, toluene, etc.
An organic compound that does not react with H4 or an alkene or alkyne compound can be used as a solvent. Although there is no particular restriction on the reaction pressure, a high pressure is desirable for equilibrium purposes, and the reaction can also be carried out in the coexistence of a gas such as hydrogen, argon, nitrogen, or helium.

The reaction formula in the present invention is generally shown, for example, as shown in the following formula.

SiH4+nC)12-CH-R-+ (R-CHz
-CHx)n SiHn-aSig4+ ncH1=C
-R-' (R-CHz-CHz)n 5iHa-n
n is reaction temperature, reaction pressure, reaction time, type of catalyst, 5iH
It can be arbitrarily controlled by reaction conditions such as the molar ratio of n and hydrocarbon.

As mentioned above, the reaction temperature ranges from 0''C to 400℃.5Reaction pressureIn view of the equilibrium of the reaction, high pressure is desirable, but it is usually 0.
The pressure is from 1000 atmospheres to 1000 atmospheres, preferably from 0 to 100 atmospheres. In addition, the charging molar ratio can be arbitrarily changed depending on the type of target product, and is not particularly critical, but it is usually (unsaturated hydrocarbon/5iHa
)・The range is from 0.01 to 100 atmospheres. Further, the reaction time can be arbitrarily selected within the range δ from several minutes to several tens of hours.

The alkylsilanes and alkenylsilanes obtained as described above contain highly reactive 5t-H bonds, and by utilizing this reactivity, silicones, silane coupling agents, silylating agents, polymers, etc. It is a novel organosilicon compound that can be expected to be used as a functional monomer and can greatly contribute to the development of functional materials.

Conventionally, these compounds have been prepared by converting alkylchlorosilanes into L
There is no other way than to obtain it by reducing it with an expensive reducing agent such as iAIH, NaAlH4, NaBHn, etc., and therefore,
Because it was extremely expensive, there was almost no development of its uses.6 The present invention fundamentally solves these drawbacks and provides a new method for producing functional monomers at low cost. .

Hereinafter, the present invention will be explained by examples.

Add 40 susol of 34 Ha to the autoclave of 21.
, 180 mmol of acetylene and 1.6 g of 0.5 wt χ of PT supported on activated carbon as a catalyst were charged.
The reaction was carried out for 6 hours at a reaction temperature of 100° C. while stirring. After the reaction was completed, volatile compounds were analyzed as gas phase components as they were, and non-volatile components were analyzed as a toluene solution using gas chromatography.

The product is C0-CH-5iHs 13.2nol (S
i based yield 33z), (CHz-CH)g Si
n< 9.2m1nol (23χ), H*5i-C
Hz-CHz-3iHs 0.8 mmol (4χ),
and trace amounts of other products were observed.

Propylene 100100 in a 500m1 autoclave
O! , heptane 20kl, as catalyst (Pφs) J
After charging 0.5 g of hCl, the temperature was raised to 80° C., and 120 mmol of SiHa was charged over 8 hours. After completion of six reactions, gas phase and liquid phase components were analyzed using a gas chromatograph.

The product is CHsCH2SiHs 16.8 mmol (
Yield on Si basis 14χ), (CHsCHzCHz)
t 5iHa 40.8 mmol (34χ) (
C1hCHtCIbh 5iH414,4mmol (
12χ) and other quantities of products were observed.

In a 500 ml autoclave, add 850 mmol of 1,3-phytagene and 200 ml of xylene. After charging 0.5 g of RuC1z (Pφ, ) as a catalyst,
The temperature was set to 105℃, and 5iHa 90a+mol
After the completion of the 0 reaction, which took 6 hours to charge, the gas phase and liquid phase components were analyzed using a gas chromatograph.

The product is R'5iHz 10.8 mmol (R' is 1
- or 2-butenyl group, yield 12χ based on Si
), R'zSiHz 27. Offimol (30χ)
, R'5SiH2, 7 mmol (3χ) and other small amounts of high boiling point by-products were observed.

The present invention uses SiH4, which has been mass-produced and can be obtained at low cost with the recent development of the anticonductor industry, as a starting material, and uses alkyl alkyl, which is expected to be a new industrial raw material for organosilicon. The silanes related to the present invention, which provide an economical and new synthetic route for silanes or alkenylsilanes, can be suitably substituted for conventional alkylchlorosilane-based basic raw materials, and are 5i- It is possible to impart high functionality due to the high reactivity of H bonds,
It also enables the development of an organic silicon industrial process that has many advantages such as being non-chlorine-based and free from corrosion.

Claims (5)

[Claims] (1) SiH_4 and at least one carbon-carbon double bond (C
=C) and/or carbon-carbon triple bond (C≡C)
A hydrocarbon compound having a number VII in the periodic table
In the presence of a catalyst consisting of a metal of Group I, Group VIA, or Group VIIA, or a catalyst containing a compound of the metal as a catalyst component,
A method for producing an organosilicon compound having a silicon-carbon bond (Si-C), which comprises carrying out a hydrosilylation reaction in a temperature range of 0°C to 400°C. (2) The organosilicon compound has the general formula R_nSiH_4_-
The method according to claim 1, which is an alkylsilane or an alkenylsilane represented by _n (where R is a hydrocarbon group and n represents 1, 2, 3 or 4). (3) The method according to claim 1, wherein the compound having a carbon-carbon double bond is ethylene, propylene, butene, isobutene, butadiene, or styrene. (4) The method according to claim 1, wherein the compound having a carbon-carbon triple bond is acetylene or propyne. (5) The method according to claim 1, wherein the catalyst is platinum, palladium, iron, cobalt, nickel, ruthenium, rhodium, or a compound thereof.