JP2501618B2 - Organosilicon compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a compound represented by the general formula (1): (However, m is 0 or a positive integer of 1 to 20, n is 1, 2 or 3, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or halogen, and R ² is alkylene having 1 to 18 carbon atoms. Group or phenylene group, R ¹ and R ² are COO
It may contain at least one functional group selected from the group consisting of H, NH2, Cl and OH. ) Relates to an organosilicon compound and a method for producing the same.

(Prior Art) An organosilicon compound is a general term for compounds having a Si—C bond, and the development of the organosilicon chemical industry is tremendous as represented by silicone (polyorganosiloxane) at present. Several methods for producing an organosilicon compound are known, and the following are typical examples.

(1) Si + RCl → R ₂ SiCl ₂ , R ₃ SiCl, RSiCl ₃ , RSiHCl ₂ (2) nRMgX + SiCl ₄ → R _n SiCl _4-n ＋ nMgXCl (3) Na + RCl + ≡Si-Cl → Si−R + NaCl (4) CH ₃ SiHCl ₂ + RCH = CH ₂ → R-CH ₂ CH ₂ Si (CH ₃ ) Cl ₂ (5) C ₆ H ₆ + HSiCl ₃ → C ₆ H ₅ -SiCl ₃ + H ₂ (6) C ₆ H ₅ -Cl + CH ₃ SiHCl ₂ → CH ₃ (C ₆ H ₅ ) SiCl ₂ + HCl (1) is a direct method of Rochow that directly produces organosilicon compounds from metallic silicon and halogenated hydrocarbons, and is the most important in the present organosilicon industry. It is a method for producing alkylchlorosilane, which is a basic material. As the halogenated hydrocarbon RCl, methyl chloride and chlorobenzene have been industrialized, and other halogenated hydrocarbons have low yields and are not industrial.

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

Although (4) is a method similar to the present invention, there is a big problem that the raw material is limited to HSiCl ₃ or CH ₃ SiHCl _{2 produced} as a by-product by the direct method.

In addition, (5) and (6) are high temperature reactions, and the raw materials are very limited such as C ₆ H ₆ , C ₆ H ₅ -Cl, CH ₂ = CHC 1, HSiCl ₃ and CH ₃ SiHCl ₂ . Limited to ones. As described above, various basic substances such as silicones, silane coupling agents and silylating agents have been developed by using the basic raw materials of the present organic silicon industry as starting materials.

However, the problems with the conventional organic silicon industrial process that uses chlorosilanes as a basic raw material are that, since it is a chlorinated system, which generally involves the generation of hydrogen chloride, the process corrosion is large, the number of reaction steps is complicated, and Due to restrictions, the methyl group is the main, and at least one of the alkyl groups is a methyl group, and so on.

On the other hand, a compound containing a silyl group (-Si _n H _{2n + 1} ) could be synthesized by reducing a compound having a trichlorosilyl group, but the reducing agent may be expensive. The use was rarely considered. Although it is possible to synthesize alkylsilanes and alkenylsilanes by hydrosilylation reaction (addition reaction) of silicon hydride compounds (Si _n H _{2n + 2} ) with alkenes or alkynes, it has been possible to obtain silicon hydride compounds in the past. However, the research was also limited because the silicon hydride compound was expensive and expensive. Zeitschrift slightly for SiH ₄
Fure Nature Forschung (Z.Naturforsc
h), 56, 444 (1950);. the, 76, 207 (1952);. Zeit Gerhard lift fur Ano Ruga Danish und Algae Neighborhood feature hemi chromatography (Z.Anorg.Allgem.Chem) 273, 275 (195
3); Journal of American Chemical Society (J.Am.Chem.Soc.) 76,3897 (1954); USPat.
2786862 (2957), etc. are the only reported cases.
According to these reports, this reaction has a reaction temperature of 400 to 5
It was as high as 00 ° C., it was a catalyst-free thermal decomposition reaction, the yield was low, and the control of the selectivity of the silane compound produced was insufficient.

There are no reports on Si ₂ H ₆ and Si ₃ H ₈ .

(Problems to be Solved by the Invention) An object of the present invention is to provide a novel organosilicon compound excellent in functionality and a method for producing the same, which does not have such problems.

(Means for Solving the Problems) The inventors of the present invention used Si as a raw material for organic silicon industry.
Focusing on ₂ H ₆ and Si ₃ H ₈ , earnest efforts were made to develop an industrial route for synthesizing an organosilicon compound from these silicon hydride compounds, and finally, by using a specific raw material, the object of the present invention was achieved. It was found that the present invention has been completed.

That is, the present invention has the general formula (1) (However, m is 0 or a positive integer of 1 to 20, n is 1, 2 or 3, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or halogen, and R ² is alkylene having 1 to 18 carbon atoms. Group or phenylene group, R ¹ and R ² are COO
It may contain at least one functional group selected from the group consisting of H, NH2, Cl and OH. ) The organosilicon compound represented by

In addition, the present invention provides the general formula CH ₂ = CR ¹ (R ² ) _m CH = CH ₂ (where m is 0 or a positive integer of 1 to 20 and R ¹ is a carbon number of 1 to 20).
Is an alkyl group, an aryl group or halogen, R ² is an alkylene group having 1 to 18 carbon atoms or a phenylene group,
R ¹ and R ² may contain at least one functional group selected from the group consisting of COOH, NH ₂ , Cl and OH. )
In the presence of a catalyst containing platinum or a compound thereof, an unsaturated hydrocarbon represented by is hydrosilylated with a silicon hydride compound represented by the general formula Si _n H _{2n + 2} (where n is 1, 2 or 3). General formula (1) characterized by (However, m is 0 or a positive integer of 1 to 20, n is 1, 2 or 3, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or halogen, and R ² is alkylene having 1 to 18 carbon atoms. Group or phenylene group, R ¹ and R ² are COO
It may contain at least one functional group selected from the group consisting of H, NH2, Cl and OH. ) Is a method for producing an organosilicon compound.

 Hereinafter, the present invention will be described in detail.

The present invention has the general formula (1) The present invention provides a novel silicon-containing compound represented by In particular, Is.

Similar compounds include allylsilane (CH
₂ = CH-CH ₂ -CiH ₃ ) Ziegler-type catalyst polymerization example can be seen (Journa of Polymer Science (Journa
l of Polymer Science), Vol31, No.122,181 (1958),
Italian patent 606018).

The silyl groups contained in these compounds are highly reactive, and C = C, C≡C, C = 0, C = N, N = C = 0, C
≡N, C = Cl, It may react with various bonds such as OH.

Utilizing this reactivity, these compounds are used as silane coupling agents, silylating agents, water repellents, etc., and the polymerizability of double bonds in the molecule is used to polymerize polymers having silyl groups. Used as a monomer for use. Polymers containing silyl groups can be used as various functional materials such as coating agents, cross-linking agents, hard coating agents and IPN. Further, the compound according to the present invention is a non-chlorine type, and has 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 of reducing a chlorosilane compound using a reducing agent LiAlH ₄ as shown in the following formula (2).

However, this method is not desirable because the reducing agent is expensive and it is difficult to obtain the alkylchlorosilane as a raw material.

An economical method is, for example, as shown in the following formula (3), Si
Hydrosilylation of dienes with H ₄ , Si ₂ H ₆ and Si ₃ H ₈ .

_{Si 2 H 6, Si 3 SiH} 4 used as a starting material is the same in the case of _{H 8, Si 2 H 6,} Ci 3 H 8 is, with the remarkable development of recent semiconductor industry, mass produced as a semiconductor gas Recently, it has become industrially available at low cost. Examples of the method for producing SiH ₄ include a method of reacting a magnesium alloy of silicon (Mg ₂ Si, etc.) with an aqueous solution of hydrohalic acid, a method of reducing silicon tetrachloride with a reducing agent such as lithium hydride, trichlorosilane. Although a method based on the above-mentioned disproportionation reaction and the like are known, for example, in the present invention, those produced by any of these methods can be preferably used. On the other hand, various dienes have been industrially produced in recent years by the development of isomerization or disproportionation reaction of double bonds of various unsaturated compounds.

The hydrosilylation reaction can be carried out by a method such as heat and light as described above, but as the present inventors have proposed (Japanese Patent Application Nos. 62-88871, 62-89888, 62-307492).
A method using a catalyst is preferable. As the catalyst, the periodic table (New Experimental Chemistry Course, published by Maruzen Co., Ltd. (1977), Group VIII, Group VIA, Group VIIA, Group VA, Group IVA, Group II
A catalyst comprising a metal of Group IA or a compound containing a compound of these metals as a catalyst constituent component. For example, Fe, Co, Ni,
Ru, Rh, Pd, Os, Ir, Pt, Cr, Mo, W, Mn, Tc, Re, S
c, Ti, V, Y, Zr, Nb, Hf or Ta or lanthanum series metal such as La or Ce, actinium series metal such as Ac or Th; Fe (CO) ₅ , Co ₂ (CO) ₃ , L ₂ Ni (olefin), L ₂ NiCl ₂ , RuCl ₃ , L ₃ RhCl, L ₄ Pd, L ₂ PdCl ₂ , I
rCl ₂ , L ₄ Pt, [(olefin) PtCl ₂ ] ₂ , H ₂ PtCl ₆・ 6H ₂
O, Ru (CO) ₂ , RuCl ₂ (Pφ ₃ ) ₃ , Cr (CO) ₆ , Mn ₂ (CO)
₁₀ (where φ is phenyl, L is PPh ₃ or PR ₃ ), (C _{5
H 5) 2 TiCl 2, (} C 5 H 5) 2 Ti (CH 3) 2, TiCl 4, (C 5 H 5) 2 Ti (CH 2 C 6
H ₅ ) ₂ , Ti (OC ₂ H ₅ ) ₄ , TiH ₂ , Ti (OC ₄ H ₉ ) ₂ (CH ₃ COCHCOC
_{H 3) 2, TiCl 3,} TiO (CH 3 COCHCOCH 3) 2, Ti (OCH (CH 3) 2) 4,
(C ₅ H ₅ ) ₂ ZrCl ₂ , (C ₅ H ₅ ) ₂ Zr (CH ₃ ) ₂ , ZrH ₄ , ZrCl ₄ , Zr (OC _{2
H 5) 4, Zr (CH} 3 COCHCOCH 3) 4, (C 5 H 5) 2 ZrH 2, (C 5 H 5) 2 ZrHC
_{l, (C 5 H 5)} 2 ZCl 2, (C 5 H 5) 2 V (CH 3) 2, V (CH 3 COCHCOCH 3) 3,
(C ₅ H ₅ ) V (CO) ₄ , V (CO) ₆ , VCl ₃ , VO (CH ₃ COCHCOCH ₃ ) ₂ , Na
(C ₆ H ₁₄ O ₃ ) ₂ V (CO) ₆ , VOCl ₃ , TaCl ₅ , TaH, Ta (OCH ₃ ) ₄ , Sm
(OOCCH ₃ ) ₃ xH ₂ O, Sm (CH ₃ COCHCOCH ₃ ) ₃ , SmCl ₃ , (C ₅ H ₅ ) ₂
HfCl ₂ , CeCl ₃ , Ce (OOCCH ₃ ) ₃ , Ce (CH ₃ COCHCOCH ₃ ) ₄ xH
₂ O, Y (CH ₃ COCHCOCH ₃ ) ₃ , YCl ₃ , Y (OOCC ₁₀ H ₇ ) ₃ , Sc (OOCCH
_{3) 3 · xH 2 O,} ScCl 3, Sc (OCH (CH 3) 2) 3, NbCl 5, Nb (OC 2 H 5)
₅ , NbH ₅ , Th (CH ₃ COCHCOCH ₃ ) ₄ , a metal complex such as ThCl ₄ , the above metal or the above metal complex supported on a metal oxide such as activated carbon, silica, or alumina, or benzoyl peroxide, azo Examples thereof include peroxides such as bisisobutyl nitrile.

The catalysts are homogeneous or heterogeneous, most of which are commercially available and readily available. Of course, these can be easily synthesized. The present invention uses the above-mentioned metal or its compound as an essential component of the catalyst, and it is of course possible to simultaneously include other catalyst components.

In the present invention, the reaction between SiH ₄ and the above-mentioned hydrocarbon is carried out at 0 to 400 ° C. in the presence of the above-mentioned catalyst.

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

The reaction temperature is 0 to 400 ° C, preferably 50 to 200 ° C, and the catalyst may be homogeneous or heterogeneous.

When the reaction is carried out in the gas phase, SiH ₄ and a method of introducing a hydrocarbon compound such as an alkene on a gas onto the surface of the solid catalyst to cause the reaction, and when the reaction is carried out in the liquid phase, for example, a liquid hydrocarbon compound containing a catalyst A method such as blowing SiH ₄ can be adopted.
In the latter case, an organic compound that does not react with SiH ₄ or an alkene or an alkyne compound such as benzene, heptane, hexane or toluene can be used as the solvent.

The reaction pressure is not particularly limited, but is preferably high pressure in equilibrium, and the reaction can be performed in the coexistence of a gas such as hydrogen, argon, nitrogen, or helium.

It is desirable that the reaction temperature is 0 to 400 ° C., and the reaction pressure is high due to reaction equilibrium, but it is usually 0 to 1000.
Atmospheric pressure, preferably 0 to 100 atmospheric pressure. Further, the charging molar ratio can be arbitrarily changed depending on the kind of the intended product, and is not particularly limited critically,
Usually, (unsaturated hydrocarbon / SiH ₄ ) is in the range of 0.01 to 100. The reaction time can be arbitrarily selected within the range of several minutes to several tens of hours.

The same applies to Si ₂ H ₆ and Si ₃ H ₈ .

(Examples) Hereinafter, the present invention will be described with reference to Examples.

Example 1 In a 500 ml autoclave, 670 mmol of SiH ₄ and CH ₂ = C (CH
₃ ) -CH = CH ₂ 1240 mmol, Pt (Pφ ₃ ) ₄ 0.21 m as catalyst
Mol was charged and the reaction was carried out at a reaction temperature of 80 ° C. for 3 hours while stirring. The reaction pressure at this time was 40 kg / cm ² . After completion of the reaction, the product main product was analyzed by gas chromatography with _{CH 2 = C (CH 3)} -CH 2 -CH 2 -SiH 3, yield 121 mmol (Si
The yield was 18% on the basis).

The following results were obtained for CH ₂ = C (CH ₃ ) -CH ₂ -CH ₂ -SiH ₃ after separation.

Elemental analysis C 59.75 H 12.20 Si 27.93 wt% Theoretical value C 59.91 H 12.07 Si 28.02 wt% IR 2150cm ^-1 (νSi-H) 890cm ^-1 (δC-H) 9
20 cm ^-1 (δSi-H) NMR 0.80 ppm (-C H ₂ -SiH ₃ ), 1.40 ppm ( -CH _2- ), 1.60 pp
m ( −CH ₃ ), 2.00 ppm (= C−C H ₂ −), 3.50 ppm (−S iH
₃ −), 4.70 ppm ( H ₂ C =) Mass 100 (M +) The above compound 15 mmol was decomposed with a C ₂ H ₅ OH solution containing LiOC ₂ H ₅ and the amount of hydrogen gas generated was quantified to be 979 ml (theoretical value: 9
86 ml).

Example 2 In Example 1, instead of CH ₂ = C (CH ₃ ) -CH = CH ₂ , Was conducted in the same manner as in Example 1 except that 810 mmol of PtCl ₂ (Pφ ₃ ) ₂ was used as a catalyst. The main product obtained is And the yield was 181 mmol (27% yield based on Si).

Elemental analysis C 74.71 H 9.21 Si 15.68 wt% Theoretical value C 74.93 H 9.15 Si 15.93 wt% IR 2150cm ^-1 (νSi-H) 890cm ^-1 (δC-H) 9
20 cm ⁻¹ (δSi—H) NMR 0.80 ppm (−C H ₂ —SiH ₃ ), 2.10 ppm ( −CH ₃ −), 2.60 pp
m (C ₆ H ₅ -C H ₂ −), 5.15 ppm (= CH ₂ ), 7.10 to 7.50 ppm
_{(P-C 6 H 4 -} ) Mass 176 (M +) The above compound 10mmol was decomposed with C ₂ H ₅ OH solution containing LiOC ₂ H _5, was quantitated hydrogen gas generation amount 642Ml (theoretical 6
It was 57 ml).

Example 3 In Example 1, 680 mmol of Si ₂ H ₆ was used instead of SiH ₄ , and 0.42 mmol was obtained by supporting 5 wt% of Pt on activated carbon as a catalyst.
(Mole number of Pt) The experiment was conducted in the same manner as in Example 1 except that it was used. The obtained main product was CH ₂ = C (CH ₃ ) -CH ₂ -CH ₂ -Si ₂ H ₅ and the yield was 27 mmol (the yield based on Si was 4%).

Elemental analysis C 45.89 H 10.98 Si 21.11 wt% Theoretical value C 46.08 H 10.83 Si 21.55 wt% IR 2150cm ^-1 (νSi-H) 890cm ^-1 (δC-H) 9
20 cm ^-1 (δSi-H) NMR 0.80 ppm (-C H ₂ -SiH ₃ ), 1.40 ppm ( -CH _2- ), 1.60 ppm
(-C H ₃ ), 2.00 ppm (= C-CH _2- ), 3.37 ppm (-S iH ₃
−), 3.40 ppm (Si H ₂ −), 4.70 ppm ( H ₂ C =) Mass 130 (M +) The above compound (10 mmol) was decomposed with a C ₂ H ₅ OH solution containing LiOC ₂ H ₅ to generate hydrogen gas. When quantified 1125 ml (theoretical value
1120 ml).

(Effects of the Invention) According to the method of the present invention, SiH ₄ that has been mass-produced with the recent development of the semiconductor industry and has become available at low cost is used as a starting material, and is expected as a new material for industrial use of organic silicon. Alkenylsilanes and economical and novel synthetic routes therefor. The silanes according to the present invention can be suitably substituted for conventional alkylchlorosilane-based base materials, and can impart high functionality due to the high reactivity of Si—H bond, and It is intended to realize the development of an organic silicon industrial process which has many advantages such as being chlorinated and having no fear of corrosion.

Claims (2)

(57) [Claims] 1. A general formula (1) (However, m is 0 or a positive integer of 1 to 20, n is 1,
2 or 3, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or halogen, R ² is an alkylene group having 1 to 18 carbon atoms or a phenylene group, and R ¹ and R ² are COOH, NH
It may contain at least one functional group selected from the group consisting of 2, Cl and OH. ) An organosilicon compound represented by: 2. A general formula CH ₂ = CR ¹ (R ² ) _m CH = CH ₂ (where m is 0
Or a positive integer of 1 to 20, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or halogen, R ² is 1 to 20 carbon atoms
An alkylene group or phenylene group of 18, wherein R ¹ and R ² may contain at least one functional group selected from the group consisting of COOH, NH ₂ , Cl and OH. ) In the presence of a catalyst containing platinum or a compound thereof with a silicon hydride compound represented by the general formula Si _n H _{2n + 2} (where n is 1, 2 or 3) Hydrosilylation is carried out, The manufacturing method of the organosilicon compound of Claim 1 characterized by the above-mentioned.