JPH02191287A - Organosilicon compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (n is 0-20; p is 2 or 3; q is 2p-1; R<1> is alkylene or phenylene; R<2> is H, alkyl, alkenyl, phenyl or naphthyl). USE:A polymerizable monomer, silylating agent and a raw material for silicones. PREPARATION:A compound shown by the formula CH2=CHR<2> is hydrosilylated with a silicon hydride compound shown by formula II.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is based on -killing % formula % (where n is an integer from 0 to 20, p is 2 or 3, and q is 2
It is an integer of p to 1, R1 is an alkylene group or a phenylene group, and R3 is hydrogen, an alkyl group, an alkenyl group, a phenyl group or a naphthyl group. ) and a method for producing the same.

(Prior art) Organosilicon compounds are a general term for compounds having a 5i-C bond in -m, and the organosilicon chemical industry is currently undergoing rapid development, as typified by silicone (polyorganosiloxane). The starting materials for the organosilicon compounds are mostly alkylchlorosilanes obtained by Rochow's direct method shown in the following formula.

Sl → R"CI → R'1SiC1t,
R"3SiC1%R"5iCh, R3SiLC1g, H3iCh, (R'C1tSi)*, R"xCISi
SiR3C1*, (R'1CISi) z , where R3 is industrially limited to a methyl group or a phenyl group. For this reason, the Grignard method is used to introduce groups other than methyl and phenyl groups, and the 11 method is used to synthesize 5t-C bonds.
^We had no choice but to resort to uneconomical methods such as the IHa reduction method. In other words, the conventional use of organosilicon compounds is
Most of the research has concentrated on compounds containing bonds, and compounds containing bonding units of alkyl groups other than phenyl groups or phenyl groups, which are involved in the present invention, have rarely been utilized.

On the other hand, in recent years, not only 5iHa but also Si! Hi, 5i
With the development of the semiconductor industry, 3H* has become mass produced and easily available at low cost.

(Problems to be Solved by the Invention) The present invention proposes 5ilH6 and 5isH as new basic raw materials.
By using s, the purpose is to provide an organosilicon compound with excellent functionality that has not been seen before.

(Means for Solving the Problems) The present inventors have developed 5iJa as an industrial raw material for organosilicon.
, 5is) Is, and worked diligently to develop an industrial route for synthesizing organosilicon compounds from this, leading to the completion of the present invention.

That is, the present invention is based on the -killing% formula% (where n is an integer of 0 to 20, p is 2 or 3, and q is 2
is an integer of 9-1, R1 is an alkylene group or a phenylene group, and C is hydrogen, an alkyl group, an alkenyl group, a phenyl group or a naphthyl group. ) is an organosilicon compound represented by the general formula 2〇H-rich CHR" (where Hp is hydrogen, an alkyl group, an alkenyl group, a phenyl group, or a naphthyl group),
CH-(R')-3iJg*-+ (where n is 0 to 20
p is an integer of 2 or 3, R1 is an alkylene group or a phenylene group. ) is a method for producing an organosilicon compound represented by the general formula % (where q is an integer of 29-1), which is characterized by hydrosilylation with a silicon hydride compound represented by %.

The present invention will be explained in detail below.

The present invention provides a novel organosilicon compound represented by the formula -% killing.

R' is an alkylene group or a phenylene group, specifically, -C1h-1(CHt)r, -(CHrh, (
CHrh, -CCubes, -(cHx+h
, (CIlt+s , (Cth++*NH!
, C0OH.

It's okay.

R8 is hydrogen, an alkyl group, a group, or a naphthyl group, -CtHs% -Csllt, Cal4q--
Alkenyl groups containing substituents such as C1Hs, -C,H, -CJII CN, CI, Br, etc., specifically -CH3, CJts ~ -C 會(l・翫-ClH1s s MHL, C0OH , CN, , ClXBr, or when m is 2, C is 2
It may also consist of different types.

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

There are several manufacturing methods, including a method of reducing a chlorosilane compound using a reducing agent LIAIH, as shown in the formula below.

Cll1ICH-(R11m 5i11(CIICHt
R”)aclzp-+-*+((2p÷1-Q)/4)
LiAlH4→C11t-CH-(R'moas5(
CHtCHtR")qc1tt++, +((2p+1-
q)/4) (LiC1+^ICIs) 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.

It can be easily obtained by using 5iJi and 5i3Hs as raw materials according to the method disclosed in Japanese Patent Application No. 62-89888 by the present inventors. That is, for example, SiH4+C
l1t-CH-(R勺-co-cow→ CHx・CH
-(R"+CIh-CHx-3ixHsC)Iz-CH
4R'+-5i*Hs+q cal-co-R''-e
CRttCR-(R'-)-3tJs-+a(CII
zCIIzll”) *In this case, PL(Pφ5)4 (φ is a phenyl group, the same applies hereinafter),
HzPtCli, PtC1x (Pφ3), Rh1l (C
o)(Pφツ)s , No(Co)i, VO(acac
) * 1, N1(Co)t(Pφs)x, W(Co
)i, Pt/C.

A method using a transition metal such as lt+/C and its compound, a radical initiator such as azobisisobutyronitrile, dibutyl peroxide, or an amine compound such as n-butylamine as a catalyst is preferably used. The reaction temperature in this case is in the range of 0 to 300°C. In addition, the six reactions that may be carried out by heating in the range of 200 to 300°C may be carried out in either the gas phase or the liquid phase.

The 5l-H bond contained in the compounds related to the present invention has excellent reactivity and can react with various functional #W groups such as 0-H. Also 5t-
The 5i bond is also easy to cleave in the presence of an alkali or thermally, and on the other hand, it has a polymerizable double bond (coordination anion polymerization, radical polymerization) in the molecule, and can be copolymerized with other olefins. Various functional polymers can be created by introducing 5i-H bonds and 5i-3i bonds into conventional carbon-based polymers. Furthermore, conventionally, the substituents for Si have mainly been methyl groups and phenyl groups, but the compounds involved in the present invention are different from methyl groups and phenyl groups, and can be used as silylating agents, silicones (especially modified silicones), etc. It can be expected to be used as a new monomer for.

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

Example 1 Si! H, 42ONm j! /sin, CxTo
84Ns+j! /win, ditertiary-butyl peroxide (DTBP) at 0.21 Ha 1 /sin
And 3ONsj of argon! After cooling and collecting the 0 reaction product passed through a reaction tube with an inner volume of 90 d and a temperature of 250°C at a flow rate of /a + in, vinyl disilane was separated by distillation, and unreacted SiO and CtHt were removed. The 0 reaction was carried out for 5 hours and 16 g of vinyldisilane (C
ll・Cll-5iJs) was obtained.

Next, 13 g of the obtained vinyldisilane (147-Peng o
1), 14g (172s+mol) of l-hexene,
0.5 g of azobisisobutyronitrile as a catalyst
(3 gaol) was placed in a micro autoclave with an internal volume of 70 m, and reaction was carried out at 100°C for 3 hours.

After the reaction is complete, the product is quantitatively analyzed by gas chromatography and separated by distillation, resulting in the following two types of compounds (
1 and ■) were obtained.

Compound →, elemental analysis value of (II),! P'H-NM
I? , mass spectrum and 0.5 g of the compound on Li0C
CJsOH including Js? Tables 1 and 2 show the amount of hydrogen gas generated when decomposed at 8fi.

The yield of the obtained compounds (ri, (n) was 2.0 g each (
The yield was 8% based on Si) and 0.8 g (yield 2% based on Si).

Example 2 13g (147++mol) of vinylsilane, 1.7
-19g Cl72m101) of octadiene, 0.5g (3-
(1) The mixture was placed in a 70 d autoclave and reacted at 100°C for 3 hours.

After the reaction, the product was quantitatively analyzed by gas chromatography and separated by distillation to obtain the following compound (II
I) was obtained. Yield 2.0g (Si based yield 6
%)Met.

Elemental analysis values of compound (II), IR, 'H-NMR, mass spectrum and compound 0.58 with Li0C,)I,
Tables 1 and 2 show the amount of hydrogen gas generated when decomposed with a C,flSOil solution containing .

Example 3 51 g (820 mmol) of Si tH, 1.9-
141 g (980 gmol) of decadiene, 3 g (18 sa
ol) Place in an autoclave with an internal volume of 500 m, and
After the 0 reaction, which was carried out at °C for 4 hours, quantitative analysis was performed using gas chromatography, and 1
5 g of CHz-CI(CHx)ssitH% was obtained.

Next, 14 g (70 saol) of the above CH*=C0(CHt)5sitllB and 0.16 g (15 sol) of azobisisobutyronitrile as a catalyst, internal volume 70
The mixture was placed in a ml micro autoclave and reacted at 100°C for 3 hours.

After the reaction, the product was quantitatively analyzed by gas chromatography and separated by distillation to obtain the following compound (IV
) was obtained. Yield: 0.8g (Si based yield: 4%)
)Met.

Elemental analysis value of compound (IV), II? , 11-N? I
I? , mass spectrum and compound 0.58 on Li0C
Tables 1 and 2 show the amount of hydrogen gas generated when decomposed with a C1HsOH solution containing Js.

Example 4 74 g (800+u+ol) of SiJ*, 144 g (1001 μmol) of 1.9-decadiene, and 3 g of azobisisobutyronitrile as a catalyst (18 layers o1)
Place in an autoclave with an internal volume of 500 Jd, and
The reaction was carried out for 4 hours.

After the reaction, the product was quantitatively analyzed by gas chromatography and separated by distillation to obtain 12 g of CHi-CH (
CHx)sshHt was obtained.

Next, the obtained CUt・CH(CHi)ssisHw is 1
0 g (43 m-ol), 1.9-decadiene at 8.9
g (62 saol), 0.16 g (1 wsol) of azobisisobutyronitrile as a catalyst was placed in a 10 dl autoclave, and reacted at 100°C for 3 hours. After the reaction, the product was quantitatively analyzed by gas chromatography. After that, the following compound (V
) was obtained. The yield is 0.6 g (yield on Si basis)
4%).

Compound (V) (D elemental analysis value, IR, IH-NMR, mass spectrum and compound 0.5 g @ Li0Ct
Tables 1 and 2 show the amount of hydrogen gas generated when decomposing with a Cx1lsOH solution containing lls.

(Effect of the invention) The present invention provides a novel organosilicon compound which can be easily synthesized by using disisilane or trisilane as a raw material, and which contains a double bond in the molecule and has polymerizability. , and also has a 5L-H bond with excellent reactivity.
By taking advantage of its high polymerizability and copolymerizing it with other olefins (introducing Si-H bonds or 5i-5L bonds), various functionalities can be imparted to existing carbon-based polymers. It is also expected to be used as a new silylation agent and raw material for silicone.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) General formula CH_2=CH-(R^1)_n-Si_p(CH_2
CH_2R^2)_qH_2_p_+_1_-_q (where n is an integer from 0 to 20, p is 2 or 3, q is 2p~
is an integer of 1, R^1 is an alkylene group or a phenylene group, and R^2 is hydrogen, an alkyl group, an alkenyl group, a phenyl group, or a naphthyl group. ) is an organosilicon compound represented by (2) A compound represented by the general formula CH_2=CHR^2 (where R^2 is hydrogen, an alkyl group, an alkenyl group, a phenyl group, or a naphthyl group) is defined by the general formula CH_2=CH-(R^1) _n-Si_pH_2_p
___+_1 (where n is an integer from 0 to 20, p is 2 or 3
, R^1 is an alkylene group or a phenylene group. )
General formula CH_2=CH-(R^1)_n-Si_p(CH_2
A method for producing an organosilicon compound represented by CH_2R^2)_qH_2_p_+_1_-_q (where q is an integer from 2p to 1).