JPH01242592A - Organosilicon compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound of the formula (m is 0 or the positive integers of 1-4; n is 2 or 3). USE:A raw material for organosilicon industry such as monomers for synthesis of polymers. PREPARATION:A hydrocarbon of the formula, HCidenticalCH, H2C=C=CH2, H2C= CH-CH=CH2, H2C=CH-CH2-CH=CH2 or H2C=CH-(CH2)2-CH=CH2 is reacted with a hydrogenated silicon compound of formula SinH2n+2 in the presence of a homogeneous or heterogeneous catalyst (e.g., Fe, benzoyl peroxide or ThCl4) at 0-400 deg.C under 0-100atm. for several min-scores hr so as to be hydrosilylated, thus obtaining the aimed compound. Furthermore, the reaction can be carried out in either gas phase or liquid phase.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an organosilicon compound represented by the formula % (where m is 0 or a positive integer from ! to 4, and n is 2 or 3). This invention relates to compounds and methods for producing the same.

(Prior Art) Organosilicon compounds are generally a general term for compounds having 5i-C bonds, and the organosilicon chemical industry is currently undergoing rapid development, as typified by silicone (polyorganosiloxane). Several manufacturing methods are known, and the following methods are representative.

(1) Si +RC1-4RxSiC1g, RzS
iCI, R31C1i, R31HC1゜(2) nRMgX +5iC14→Rn5iC14−
, +nMgXC1(3) Na+RC! +=Sr-C
I-45i-R+NaC1(4) CHiSiHC
lt + RC)l-CHyo→R-CHzCHzSi(
CHi)C1m(1) is a Rocho direct method to directly produce organosilicon compounds from metallic silicon and halogenated hydrocarbons, and it produces alkylchlorosilanes, which are the most important basic raw materials in the current organosilicon industry. This is a method of manufacturing. As halogenated hydrocarbon RCl,
Methyl chloride and chlorobenzene have been industrialized, and other halogenated hydrocarbons have low yields and are not industrially viable.

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.

Therefore, (4) is a method similar to the present invention, but the raw material is H5iC1, and C)lssiRc which is a by-product in the direct method.
There is a big problem that it is limited to lz etc.

In addition, (5) and (6) are both high-temperature reactions and are limited to very limited raw materials such as CHsSiHClg.

As mentioned above, most of the basic raw materials in the current organosilicon industry are methyl or phenylchlorosilanes, and these silicon compounds are used as starting materials to produce various silicones, silane coupling agents, silylating agents, etc. Functional substances have been developed.

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

On the other hand, compounds containing a silyl group 1' [(-5inH There was little to think about.

It is possible to synthesize alkylsilanes and alkenylsilanes by hydrosilylation reaction (addition reaction) between SiH4 and alkenes or alkynes, but conventionally SiH4
Because it was difficult and expensive to obtain, there was little research into it. Slightly Zeitschrift fair Naturforsch (Z, Naturforsch,
), Tadashi, 444 (195G); ibid.

i, 207 (1952): Zeitschrift Fair Anorganische Land Allgemeine Hemi-
(Z, Anorg, Allgeei, Chem,)g]
Engineering 275 (1953): Journal on
American Chemical Society 4 (J, As
, Chem, Soc, ) Ko'f1. 3897(
1954); U, S, Pat.

2786862 (1957), etc. According to these reports, the reaction temperature is as high as 400 to 500°C, the reaction is non-catalytic and thermally decomposed, and the yield is low (, The selectivity of the silane compound used was also insufficiently controlled.

There are no reports regarding SiJ* and 5iaH*.

(Intelligence B to be Solved by the Invention) An object of the present invention is to provide a new organosilicon compound with excellent functionality and a method for producing the same, which is free from such problems.

(Means for Solving the Problems) The present inventors have discovered that 5iJ-
Or, focusing on 5isHs, they worked hard to develop an industrial route for synthesizing organosilicon compounds from these hydrides, discovered that the objects of the present invention could be achieved by using specific raw materials, and completed the present invention. I ended up letting it happen.

That is, the present invention is an organosilicon compound represented by the general formula CHz-CH (CHz)a 5inHz*++ (where m is 0 or a positive integer from 1 to 4, and n is 2 or 3), and further, HC=CH
, HtC-C-CL , HiC=CII-CIIIGH
z -HzC"CH-CHt-CH-CHt or Hz
C=CI-(CHz) 1-CHmCHt, -Formula 5
General formula % characterized by hydrosilylation with a silicon hydride compound represented by inH□ or (where n is 2 or 3) (where m is O or a positive integer from 1 to 4, n is a method for producing an organosilicon compound represented by 2 or 3)'.

The present invention will be explained in detail below.

The present invention is general 2CH1-CI-(Cut)s-3!
n) It provides a novel organosilicon compound represented by Its-+. Specifically, CHt”CB-5ltHs%
CH, -CH-CHtSizHs, CL=CFl-(C
elt) tsiJs s C) ft-C) I-(CH
g) ssiJs, CH*=lCH-(CHg)asis
Ht, cHt, cH-stsut, CHt=CH-CH
Similar compounds such as tSisH, allylsilane (CHg-CH-Cl鵞-5iFI3) have been used in the past.
), there are only examples of polymerization using Ziegler-type catalysts (
Journal Opbolymer Science
of PolymerScience), Vol.
31. Na122.181 (1958), Italian Patent No. 60601B).

The silyl groups contained in these compounds are highly reactive,
C dew c, c=c, c-o, C Tomi N, Nmaro C song 0, CmN
5 C Tomi CI.

It can react with the bonds of seeds such as. These compounds utilize this reactivity to perform silane coupling, silylating agents,
It is used in saltwater agents and the like, and is also used as a monomer for polymerizing polymers having silyl groups by utilizing the polymerizability of double bonds within the molecule. Polymers containing silyl groups can further be used as various functional materials such as coating agents, crosslinking agents, partconide polymers, and IPH. Furthermore, the compounds related to the present invention are non-chlorine-based and have no process problems such as corrosion.

Next, a method for producing the compound according to the present invention will be described.

There are several manufacturing methods, for example, a method in which a chlorosilane compound is reduced using reduction 1?fi L i A IPI 4 as shown in the following formula.

CHzlICH-(CL) --5inC1g-,t
+ ((2n + 1) /4) LiAIHa→CH
1sCH-(Cut)@-3inHxa*++((2
n+1)/4)LiC1+((2n+1)8)AICI
! CI) However, this method cannot be said to be a desirable method because the reducing agent is expensive and it is difficult to obtain chlorosilane as a raw material.

An economical method is as shown in the formula (I[) below, 311H&
, hydrosilylation of dienes with 5isHs.

CHg-CH-(CHm)-Ichitomi-CH-C1h+5i
ttl*→Cf1tllCI+-(CIlg)-m-C
The same is true for Hm-CHt-5ttHs (II)SisHs. 5iJi and SiJ*, which are used as raw materials, have been mass-produced as semiconductor gases due to the remarkable development of the semiconductor industry in recent years, and have recently become industrially inexpensive. It is now available. As a method for producing Si*Hi, 5tsHs, for example, silicon magnesium alloy (+'
+g, st, etc.) with an aqueous solution of hydrohalic acid, and a method of reducing hexachlorodisilane or octachlorotrisilane with a reducing agent such as lithium hydride are known. Those produced by this method can also be suitably used. On the other hand, in recent years, a variety of α,ω-dienes have come to be industrially produced by the development of double bond isomerization or disproportionation reactions of various unsaturated compounds.

The hydrosilylation reaction can be carried out by heat, light, or other methods as described above, but as previously proposed by the present inventors (Japanese Patent Application No. 62-88871, No. 62-89888,
62-307492) A method using a catalyst is preferable; examples of the catalyst include Group 1, Group ■A in the periodic table (New Experimental Chemistry Course, published by Maruzen Co., Ltd. (1977))
Catalysts consisting of metals of Group ■A, Group VA, Group 1VA, Group ■A, or catalysts containing compounds of these metals as catalyst constituents. For example, Fe, Co, Ni, Ru
%Rh, Pd, Os, Ir%Pt, Cr, M
o, H1Mn%Tc, Re5Sc, Ti, V
% Y s Zr, Nb, Hf or Ta or metals such as lanthanum series metals such as La and Ce, actinium series metals such as Ac and Th; Fe (Co)
s, Cot (Co) s, LJi (olefin),
LiNiC1x, RuC15, LJhCl, LaP
dS LxPdC1-rich, IrC1m, L4Pt,
((olefin) PtC1z) t, HzPtC
1* ・6HxO, Ru(Co)i, RuC1x(
Pφ3)2, Cr(Co)a, Moa(CO)+s
(However, φ is phenyl, L is PRhs or PH1
), (CJs)tTic1寞, (C-sHs) gTi (
CH3) z, (CsHs)xTi(CHzCJs)t
, TiCl4, Ti(OCJs)4, Tin5. T
i(OCJJi(CIbCOCHCOCHs)i,T
iCh, Ti0(C)lscOcHcOcH3) *
, Ti (OCH(CH3) ri 4, (CsL)
rC11, (CsHs) tZr (CHs) z,
ZrH4, ZrCL, Zr(OC,H,),, Zr(
CHaCOCflCOCHi)4, (CsHs)tZr
Ht, (CsHs)tZrHcl, (CsHs)
*VC1g, (CsHs)iV(CHs)z, V(C
)IsCOCHCOCHs)s-(CsHs)V(Co
) a, V(CO) &, VCl5, VO(CHsCOCl
lCOCHi)i, Na(CJ+40s)tV(CO
)ilVOCIs, TaCl5s Ta1l,
Ta(OCRs)4.5s(OOCCIIa)s
・ xHHO25ll (CHiCOCHCOCHi)
x, 5LIch, (CsHs)JfCh, CeC
11, Ce(OOCCHs)z, Ce(CLCOCH
COCHs)s ・xHzOlY(CH3COCHC
OCH3) x, YCIs, Y(00CC+Jth, 5
c(OOCCHs) s' XI! 01ScC1s
, 5c(OCH(CHs)*)s, NbCl5,
Nb(OCzHs)s, NbHs%Th(CLCOC
Examples include metal complexes such as HCOCL)4 and ThC14, the above-mentioned metals or the above-mentioned metal complexes supported on metal oxides such as activated carbon, silica, and alumina, and peroxides such as benzoyl peroxide and azobisisobutylnitrile. It will be done.

Catalysts can be homogeneous or heterogeneous, and most of them are commercially available and readily available. Of course, these 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 contain other catalyst components at the same time.

In the present invention, the reaction between 5izHh s 5isH- and the above-mentioned hydrocarbon is carried out in the presence of the above-mentioned catalyst.
It is carried out at 00°C.

This 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.

Reaction temperature is 6-400°C, preferably 50-200°C
The catalyst can be either homogeneous or heterogeneous.

When the reaction is carried out in the gas phase, Si, H, or 5isH
- A method of introducing and reacting a hydrocarbon compound such as a gaseous alkene or alkyne onto the surface of a solid catalyst. When carrying out the reaction in a liquid phase, for example, 5ixt is added to a liquid hydrocarbon compound containing a catalyst.
Methods such as injecting H or Si3N can be adopted. In the latter case, benzene, heptane, hexane,
5iJa s 5isHs such as toluene or an organic compound that does not react with alkenes or alkyne compounds can be used as a solvent. There is no particular restriction on the reaction pressure, but a high pressure is desirable for equilibrium, and hydrogen, argon, nitrogen, It can also be carried out in the presence of a gas such as helium.

As mentioned above, the reaction temperature is 0 to 400°C, and the reaction pressure is preferably high from the viewpoint of reaction equilibrium, but usually 0 to 1
00 atm, preferably 0 to 20 atm.

Furthermore, the charging molar ratio can be arbitrarily changed depending on the type of target product, and is not particularly critical, but usually (unsaturated hydrocarbon/5tli- or 5iJs)-0 ,01-100. Moreover, the reaction time can be arbitrarily selected within the range of several minutes to several tens of hours.

(Example) Hereinafter, the present invention will be explained by examples.

Example 1 In a 100-meter autoclave, 5i21 (6 was placed at 141 m
mol, 1.5-hexadiene 261m+sol
, a poly T-mercaptopropylsiloxane-Pt complex supported on Sing as a catalyst (Pt supported amount 2
．． 4 wt%) was charged in an amount of 0.1 sa+ol (amount of Pt), and the mixture was reacted for 2 hours at a reaction temperature of 80°C with stirring.

The reaction pressure at this time was 6 Kg/d. After the reaction was completed, the product was separated and fractionated using a gas chromatograph, and C) Iz=CI(CHz)4-5iJs was 5*@ol(
A yield of 4% (based on Si) was obtained.

The following results were obtained regarding CHt-CH(CHt) a-3izHs after separation.

Elemental analysis C49,78H12,31Si 37.69
wt%C49,92H11,17Si 38.91w
t%IRv 5i-H2150C11-cage δ5i-H940cta-''HNMR (100MHz) 0.8ppm (-C且□-3iHm-), 1
．． 40ppm (-)2.10ppm (-CH-C
L-), 3.37ppm+(-5tHs), 3.40
ppm(-3ing-), 4.90-5.301)l
) II (LLC-CI-) Mass 144 (M
”) The above compound 1.5*@ol was converted into CJ containing Li0CtHs.
It was decomposed with an sOH solution and the amount of hydrogen gas generated was determined to be 161Id (theoretical value 168m).

Example 2 In 21 autoclaves, 51! 50m5ol of Hh,
Acetylene 160s+gol, PtC1z as catalyst
(PΦ1) was charged and reacted for 5 hours at a reaction temperature of 100°C with stirring. After the reaction, volatile compounds were analyzed as gas phase components as they were, and non-volatile components were analyzed using a gas chromatograph as a toluene solution. Separate and fractionate, C)!
211@01 (3% yield on Si basis) of i.cH-5ixHs was obtained.

C11l・CH-3i after separation! Regarding Hs, the following results were obtained.

Elemental analysis C27,1L H9,32Si 61.94
@t% theoretical value C27,22H9,14Si 63.
65 wt%IRy 5t-H2150C1-'δ5i-H940cm-''IINMR (100MHz) 3.37ppm (-3in寞-3iH1), 3.7
8ppm (-3υji-3iHa), 4.90~5
．． 30p, ■c! hc bow 1-) Mass 88 (M
”) The above compound 1 sv+ol was replaced with C containing Li0CzHs,
It was decomposed with a H,O)I solution and the amount of hydrogen gas generated was determined to be 105 d (theoretical value 112 d).

Example 3 113s+m of 5iJs in a 100d autoclave
ol.

280 m*ol of 1.5-hexadiene, 50 i of xylene, and 0 of the same catalyst used in Example 1.
．． After charging 5 g, the temperature was set to 100°C and the reaction was carried out for 2 hours. After the reaction was completed, the product was separated and fractionated using a gas chromatograph, and 3.4 vw of C1h-CH-(CHz) 4-5iJt was added.
ol (yield 3% based on Si) was obtained.

CHz・CI after separation (-(C)I) 4-3i3H
Regarding No. 1, the following results were obtained.

Elemental analysis C41,17H10,51Si 48.15
Wt% theoretical value C41,31H10,40St 48.
29gt%IRySi-H2150cm-'δ5i-H940Ca+-''HNMR o, spp■ (-C and □-3t), 1.40p
pm(-Cdan, ), 2.10ppm(・CH-川x-
), 3.18pp■ (-5t Danyoichi 3t), 3.
37pp ■ (-3ins), 3.401) pH (
-CHt-5ijjl-) 4.90 to 5.30 ppm (
Mass (M''')174 0.5m+mol of the above compound Ct containing Li0CJs
It was decomposed with HsOH solution and the amount of hydrogen gas generated was determined to be 72d (theoretical value 78Id).

(Effects of the Invention) According to the method of the present invention, 5iJi, which has been mass-produced with the recent development of the semiconductor industry and has become available at low cost, can be used.
Alternatively, using 5LJs as a starting material, it is possible to provide alkenylsilanes that are expected to be new industrial raw materials for organosilicon and an economical and new synthetic route for the same.
The silanes according to the present invention can be suitably substituted for conventional alkylchlorosilane-based basic raw materials, and S
Due to the high reactivity of the i-H bond, it is possible to impart high functionality, and since it is non-chlorine-based, there is no need to worry about corrosion.
The aim is to realize the development of an organosilicon industrial process with the following advantages.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) Organosilicon compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where m is 0 or a positive integer from 1 to 4, and n is 2 or 3). (2) HC≡CH, H_2C=C=CH_2, H_2C
=CH-CH=CH_2, H_2C=CH-CH_2-
CH=CH_2 or H_2C=CH-(CH_2)_
2-CH=CH_2, the general formula SinH_2_n_+_
2 (where n is 2 or 3) A general formula characterized by hydrosilylation with a silicon hydride compound ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, m is 0 or a positive number from 1 to 4) n is an integer of 2 or 3).