JPH0733881A - Production of polyorganosilane - Google Patents

Abstract

PURPOSE:To safely, easily obtain the objective silane by a reaction using a single vessel through heterogeneous reaction of a specific disilane compound in the presence of an alkali metal hydrocarbinolate. CONSTITUTION:A disilane compound of formula I [R<1> and R<2> are each (substituted) monovalent hydrocarbon; n is 0-5] is reacted for a time enough to form a polyorganosilane in the presence of an alkali metal hydrocarbinolate of formula MOR<3> [R<3> is (substituted) monovalent hydrocarbon; M is alkali metal] followed by reaction of the resultant reaction system with an organohalosilane of formula II [R<4> is (substituted) monovalent hydrocarbon or hydrocarbyloxy; X is halogen; m is 1-3], thus affording the objective silane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polyorganosilane. More specifically, it relates to a method for easily and safely introducing an arbitrary organic group into polyorganosilane.

[0002]

Polyorganosilanes are organic conductive materials,
It is known to be useful as a nonlinear optical material, a photolytic initiator, a silicon carbide precursor, a photoresist material, etc. (for example, Miller, RD; Michl, J., Chem. Re.
v., 89, 1359 (1989)). As a method for producing polyorganosilane, the Wurtz method using organohalosilane or organohalodisilane as a starting material is widely used.
However, the Utur method is dangerous because it uses metallic sodium and metallic potassium that are self-igniting in air, and the reaction conditions are strict, making it difficult to introduce substituents other than alkyl and aryl groups. There is a drawback that.

Several attempts have been made to solve these drawbacks. For example, Barnes et al. Have added vinyl magnesium bromide to a methylpolysilane mixture containing an alkoxy group synthesized by a disproportionation reaction of an alkoxydisilane. To give a vinyl group-containing polysilane (US Pat. No. 5,025,07).
No. 5 specification).

Wilfried et al. Contain a methyl group and a phenyl group by disproportionating a mixture of a methoxydisilane derivative in which an organic group bonded to a silicon atom is a methyl group and a phenyl group, with sodium methoxide. A polyorganosilane is obtained (JP-A-4-27).
0730 publication).

Imai et al. Have described triorganotrialkoxydisilane and diorganotetraalkoxydisilane as
Disclosed is a method for producing a polyorganosilane by carrying out a disproportionation reaction in the presence of an alkali metal hydrocarbinolate. (JP-A-4-311727).

The disproportionation reaction using such an alkoxydisilane compound is excellent in that the reaction can be carried out under mild conditions without using sodium metal or potassium metal. So far, some polyorganosilanes have been used. Has been obtained. However, when considering the use of polyorganosilane for nonlinear optical materials, photoresists, etc.,
Further, it is desired to easily synthesize polysilane having various organic groups.

The polyorganosilane having such various organic groups is introduced into a raw material disilane compound as desired by the above-mentioned Wilfried and Imai et al. To carry out a disproportionation reaction. It is possible to get by. However, to obtain a disilane compound having such an organic group, selective reaction of a certain number of halogen atoms or alkoxy groups present in the disilane compound with a reagent having an organic group to be introduced selectively gives a specific compound. There are practical problems in that it is difficult to introduce an organic group, and the disilane compound having the organic group that is formed has a high boiling point and is difficult to purify by distillation. Also, the two-step reaction as in Barnes et al. Is complicated.

On the other hand, although organochlorosilanes having various organic groups are easily available, a method for obtaining a substituted polysilane safely and easily from such organochlorosilanes is not known.

[0009]

The present invention has been made to solve such a situation, and the object of the present invention is to provide polyorgano having various organic groups which are easily used as materials for the above-mentioned uses. To provide a method for producing a silane, in particular, a polyorganosilane having a vinyl group which can be crosslinked by a hydrosilylation reaction, from easily available disilane and halosilane simply by a series of reactions using a single container and safely. Is.

[0010]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have conducted a disproportionation reaction of a disilane compound in the presence of a metal carbinolate and then reacted with an organohalosilane. The inventors have found that the problems can be solved by the above and completed the present invention.

That is, the method for producing the polyorganosilane of the present invention comprises the following formula: R ¹ _n Si ₂ (OR ² ) _6-n (I) (wherein R ¹ and R ² are the same or different substituents). Alternatively, it represents an unsubstituted monovalent hydrocarbon group, and n is 0.
A disilane compound represented by the formula: MOR ³ (II) (wherein R ³ represents a substituted or unsubstituted monovalent hydrocarbon group, and M represents an alkali metal). And reacting in the presence of an alkali metal hydrocarbinolate for a time sufficient to form a polyorganosilane; the reaction product system is then added to the general formula: R ⁴ _m SiX _4-m (III) ( In the formula, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group or carbyloxy group; X
Are the same or different halogen atoms, m is 1 to 3
Of the organohalosilane represented by the formula (1) is obtained, and a polyorganosilane having an R ⁴ —Si group in the molecular chain is obtained.

In the disilane compound (I) used as one of the starting materials in the present invention, the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom represented by R ¹ is, for example, methyl or ethyl. Linear or branched alkyl groups such as propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl; cycloalkyl groups such as cyclohexyl; benzyl, 2-phenylethyl, 2-phenylpropyl, 3-
Aralkyl groups such as phenylpropyl; aryl groups such as phenyl, tolyl, mesityl; alkenyl groups such as vinyl and allyl; alkenylaryl groups such as p-vinylphenyl and p- (2-propenyl) phenyl; arylalkenyl groups such as styryl. And halogenated hydrocarbon groups such as chloropropyl, chlorophenyl and 3,3,3-trifluoropropyl, and various substituted hydrocarbon groups such as p-methoxyphenyl group. These may be the same as or different from each other. A methyl group is particularly preferred because it is easy to synthesize and the boiling point of the disilane compound is relatively low and therefore easy to handle.

R ² is a monovalent hydrocarbon group constituting a hydrocarbyloxy group which is a silicon functional group, and is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl; cyclohexyl. Examples include cycloalkyl groups such as; aryl groups such as phenyl and tolyl; alkenyl groups such as allyl. Methyl, ethyl, n-propyl,
An alkyl group such as isopropyl and a phenyl group are preferable, and a methyl group or an ethyl group is more preferable.

Specific examples of such a disilane compound include pentamethylmethoxydisilane, pentaethylmethoxydisilane, and 1,1,1,2-tetramethyl-2-n.
-Hexyl-2-methoxydisilane, 1,1,1,2-
Tetramethyl-2-phenyl-2-methoxydisilane,
1,1,1,2-tetramethyl-2-vinyl-2-methoxydisilane, 1,1,1,2-tetramethyl-2-cyclohexyl-2-methoxydisilane, 1,1,1,2
-Tetramethyl-2-tert-butyl-2-methoxydisilane, 1,1,1-trimethyl-2,2-diphenyl-
2-methoxydisilane, 1,1,1-trimethyl-2,
2-di-n-hexyl-2-methoxydisilane, 1,
1,2,2-tetramethyl-1-phenyl-2-methoxydisilane, 1,1,2-trimethyl-1,2-diphenyl-2-methoxydisilane, 1,1-dimethyl-1,
2,2, -triphenyl-2-methoxydisilane, 1,
2,2-trimethyl-1,1-diphenyl-2-methoxydisilane, 1,2,2-triethyl-1,1-diphenyl-2-methoxydisilane, 1,2-dimethyl-1,
Monomethoxydisilane compounds such as 1,2-triphenyl-2-methoxydisilane, 1-methyl-1,1,2,2-tetraphenyl-2-methoxydisilane; 1,
1,2,2-tetramethyl-1,2-dimethoxydisilane, 1,1,2,2-tetraethyl-1,2-dimethoxydisilane, 1,1,2,2-tetraphenyl-1,2
1,2-dimethoxydisilane, 1,1-dimethyl-2,2-diphenyl-1,2-dimethoxydisilane such as
-Dimethoxydisilane compound; 1,1,1,2-tetramethyl-2,2-dimethoxydisilane, 1,1,1-trimethyl-2-phenyl-2,2-dimethoxydisilane, 1,1,2-trimethyl- 1-phenyl-2,2-
Dimethoxydisilane, 1,1-dimethyl-1,2-diphenyl-2,2-dimethoxydisilane, 1,2-dimethyl-1,1-diphenyl-2,2-dimethoxydisilane, 1-methyl-1,1,2 -Triphenyl-2,2-
Dimethoxydisilane, 2-methyl-1,1,1-triphenyl-2,2-dimethoxydisilane, 1,1,1,2
1,1-dimethoxydisilane compounds such as tetraphenyl-2,2-dimethoxydisilane; 1,1,2-trimethyl-1,2,2-trimethoxydisilane, 1,1
-Dimethyl-2-phenyl-1,2,2-trimethoxydisilane, 1,2-dimethyl-1-phenyl-1,2,
2-trimethoxydisilane, 1-methyl-1,2-diphenyl-1,2,2-trimethoxydisilane, 2-methyl-1,1-diphenyl-1,2,2-trimethoxydisilane, 1,1, 1,1,2-Trimethoxydisilane compounds such as 2-triphenyl-1,2,2-trimethoxydisilane; 1,1,1-trimethyl-2,2,2-
Trimethoxydisilane, 1,1-dimethyl-1-phenyl-2,2,2-trimethoxydisilane, 1-methyl-
1,1,1-trimethoxydisilane compounds such as 1,1-diphenyl-2,2,2-trimethoxydisilane and 1,1,1-triphenyl-2,2,2-trimethoxydisilane; 2-dimethyl-1,1,2,2-tetramethoxydisilane, 1-methyl-2-phenyl-1,
1,1,2,2-tetramethoxydisilane compounds such as 1,2,2-tetramethoxydisilane, 1,2-diphenyl-1,1,2,2-tetramethoxydisilane;
1,1-dimethyl-1,2,2,2-tetramethoxydisilane, 1-methyl-1-phenyl-1,2,2,2-
Tetramethoxydisilane, 1,1-diphenyl-1,
1,1, such as 2,2,2-tetramethoxydisilane
1,2-tetramethoxydisilane compounds; pentamethoxydisilane compounds such as methylpentamethoxydisilane, phenylpentamethoxydisilane; and hexamethoxydisilane; and methoxy groups in some or all of these compounds are ethoxy, n-propoxy, Examples thereof include those substituted with other hydrocarbyloxy groups such as isopropoxy and phenoxy.

Such disilane compounds include hydrocarbyloxylation of halogenated disilane compounds, such as alkoxylation or aryloxylation; alkyl groups and other organic groups on halogenated disilane compounds or hydrocarbyloxylated disilane compounds with organometallic reagents. Introduction; can be synthesized by a known method such as chlorination of an alkyl or aryl disilane compound and subsequent hydrocarbyl oxylation, for example, alkoxylation or aryl oxylation. For example, Experimental Chemistry Course No. 12
Volume, Organometallic Compounds (Maruzen), 3rd Edition, Chapter 16, 33
The reactions detailed on pages 1-377 may be utilized. Among these starting disilane compounds, chlorinated disilanes can be obtained, for example, as a by-product of a direct synthesis method of organochlorosilanes or a redistribution reaction product of the by-product.

In the alkali metal carbinolate (II) used as a catalyst in the present invention, examples of the alkali metal represented by M include lithium, sodium, potassium, rubidium and cesium. Sodium and potassium are preferred. Examples of the monovalent hydrocarbon group represented by R ³ include those similar to R ² in the above general formula (I), and a lower alkyl group such as methyl, ethyl and tert-butyl is used in view of reactivity. Is preferred.

Specific examples of the alkali metal hydrocarbinolate (II) used in the present invention include sodium methylate, sodium ethylate and potassium tert.
-Butyrate, sodium phenolate and the like. Further, the lithium alcoholate synthesized in the reaction system from n-butyllithium and alcohol can be used as it is.

The amount of the alkali metal hydrocarbinolate is not particularly limited, and 0.001 to 100 mol% can be used with respect to the disilane compound (I) used. However, if the amount of the catalyst is too small, the reaction becomes very slow, and if it is too large, it becomes difficult to remove the catalyst after the reaction and it is economically disadvantageous. The catalyst amount is preferably 0.1 to 30 mol% with respect to the disilane compound (I).

In the organohalosilane (III) used as the second step reaction reagent in the present invention, the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom represented by R ⁴ is as described above. What was illustrated about R < ¹ > in general formula (I) is mentioned. Furthermore, a hydrocarbyloxy group may be used as R ⁴ , and examples of such a hydrocarbyloxy group include a linear or branched alkoxy group such as propoxy and butoxy; and an aluroxy group such as phenoxy. It Multiple R
^{If 4} are bonded to the same silicon, they may be the same or different.

When the desired substituent is introduced, it is generally easier to introduce it into the organohalosilane than to introduce it into the disilane compound, and the boiling point of the organohalosilane is generally above. Since it is lower than that of the disilane compound corresponding to, it can be easily purified even if R ⁴ is thermally unstable. Therefore, preferable R ⁴ includes methyl, ethyl, tert-butyl, n-hexyl, phenyl, p-tolyl, vinyl, p-vinylphenyl, styryl and 3,3 depending on the intended use of the polyorganosilane. , 3-trifluoropropyl, etc., and R ⁴ is R
The method of the invention is advantageous when it is desired to introduce groups different from ¹ into the polyorganosilane, for example when R ¹ is a methyl group and R ⁴ is an organic group other than a methyl group. R ⁴ is a heat-labile group such as a vinyl group, or a phenyl group or p-
It is particularly preferred to employ the invention in the case of groups such as vinylphenyl groups which are so large that they significantly raise the boiling point of the disilane.

X is a halogen atom such as fluorine, chlorine, bromine or iodine. From the viewpoint of reactivity and easiness of synthesis, X, chlorine, bromine or iodine atom is preferable, and chlorine atom is most preferable.

Specific examples of such organohalosilane (III) include trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane,
Triphenylchlorosilane, dimethylvinylchlorosilane, methyldivinylchlorosilane, trivinylchlorosilane, dimethyl (p-vinylphenyl) chlorosilane,
Dimethylstyrylchlorosilane, dimethyl-n-hexylchlorosilane, methylvinylphenylchlorosilane,
Monochlorosilane compounds such as dimethyl-n-propoxychlorosilane, dimethylisopropoxychlorosilane, dimethylphenoxychlorosilane; dimethyldichlorodilane, methylphenyldichlorosilane, diphenyldichlorosilane, methyl-n-hexyldichlorosilane, methyl-tert-butyldichlorosilane. Dichlorosilane compounds such as, methylvinyldichlorosilane, divinyldichlorosilane, methyl (p-vinylphenyl) dichlorosilane, methylstyryldichlorosilane, methylphenoxydichlorosilane; methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane. Chlorosilane, vinyltrichlorosilane, n-hexyltrichlorosilane, cyclohexyltrichlorosilane, tert-butane Le trichlorosilane, (p
-Vinylphenyl) trichlorosilane, trichlorosilane compounds such as styryltrichlorosilane; and their corresponding bromosilanes, iodosilanes and the like.

Such an organohalosilane (III) is
It can be obtained from a metal silicon and a monohalogenated hydrocarbon by a direct synthetic method, or can be synthesized by alkylating or arylating the organohalosilanes thus obtained. Alternatively, known methods such as Grignard reaction of halosilane, hydrosilylation reaction of silane having Si-H group, reaction of organic chloride to halosilane in the presence of aluminum chloride may be used to introduce desired R ^4. You can Further, in order to obtain an organohalosilane having a desired number of halogen atoms, a disproportionation reaction in the presence of a Lewis acid can be used.

The number of hydrocarbyloxy groups in the disilane compound (I) and the number of halogen atoms bonded to silicon atoms in the organohalosilane (III) are selected depending on the molecular structure and molecular weight of the target polyorganosilane. It For example, monoalkoxydisilane or 1,2
A disproportionation reaction is performed using a dialkoxydisilane, and then a mono- or dihalosilane is reacted to obtain a chain-like or cyclic polyorganosilane having various organic groups introduced therein. Further, a branched or reticulated polyorganosilane can be obtained by using a disilane compound having two or more alkoxy groups at the same silicon atom in the disilane compound as a raw material or using trihalosilane.

Furthermore, in some cases, two or more kinds of disilane compounds and / or organohalosilane compounds are used, respectively, to combine any of various organic groups to synthesize polyorganosilane having various organic groups. It is also possible.

It is considered that the organohalosilane reacts with the silyl sodium group at the terminal of the polysilane molecule produced by the disproportionation reaction in the first step, and therefore the amount of the organohalosilane is related to the amount of the metal hydrocarbinolate. That is, it is sufficient that the amount of the organohalosilane is equal to or less than that of the metal hydrocarbinolate.

The reaction is carried out by mixing the starting disilane compound (I) with the alkali metal hydrocarbinolate (II), and when the disilane compound disappears or after aging the reaction, the organohalosilane compound (III). Proceed by mixing. That is, in the first step, the disproportionation reaction of the disilane compound gives a polysilane compound having a sodium atom bonded to the end of the molecular chain, and then the desalting reaction of the second step is continuously carried out in the same container. Although the mixing method is arbitrary, a disilane compound or an organohalosilane may be slowly added dropwise in order to prevent the reaction from rapidly occurring.

A reaction solvent may be used to promote the reaction smoothly. Examples of the reaction solvent include hydrocarbon solvents such as toluene, xylene, n-hexane, n-heptane, and cyclohexane; diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc. Examples of suitable ether solvents include aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric triamide.

Raw material disilane compound (I), alkali metal hydrocarbinolate (II), sodium-terminated polysilane compound produced in the first step, by-product alkoxysilane compound, and organohalosilane (III) added in the second step Is easily decomposed by the reaction with water. Therefore, the reaction is carried out in a substantially anhydrous state. The reaction is usually -80 to 250 in both the first stage and the second stage.
C., preferably in the range of 20 to 150.degree. The reaction temperature can be determined by the relationship among the disilane compound, the reaction solvent, the amount of catalyst, and the molecular weight of the desired polyorganosilane. The reaction is preferably carried out under the pressure of ambient atmosphere. However, higher or lower pressures can be applied if desired.

The sodium chloride produced and the unreacted catalyst were separated by filtration, and the by-produced alkoxysilane compound, the residual catalyst and the unreacted organohalosilane were removed by a method such as distillation to obtain the reaction product. The polyorganosilane is isolated.

[0031]

INDUSTRIAL APPLICABILITY According to the present invention, the disilane compound used as a raw material has one or more organic groups in the molecule and the organohalosilane compound has 1 in the molecule.
The polyorganosilane having an arbitrary organic group bonded to a silicon atom can be synthesized by arbitrarily selecting one kind or two or more kinds of organic groups. Especially when the synthesis of disilane compound is difficult, when the organic group of disilane is thermally unstable and it is difficult to purify, and when the reactive organic group in the generated polyorganosilane is also thermally unstable. For example, a substituent can be safely and easily introduced into a target polyorganosilane. Although the reaction has two stages, a series of reactions can be carried out by a single vessel.

According to the method of the present invention, a wide range of substituted or unsubstituted 1-bonded to a silicon atom such as phenyl group, vinyl group, p-vinylphenyl group, styryl group, trifluoropropyl group as well as methyl group can be obtained. It is possible to safely produce a polyorganosilane having a chain or other silicon-silicon skeleton having a valent hydrocarbon group.

The polyorganosilane having a reactive organic group, particularly a vinyl group, in the molecule obtained by the present invention can be used as a raw material to have a higher molecular weight or a crosslinked polymer. Further, in the case of the present invention, by arbitrarily selecting the chain length or the degree of polymerization of the polysilane formed by the disproportionation reaction in the first step, an arbitrary amount of the reactive organic group is present in the molecule. ,
The crosslink density can be controlled arbitrarily.

The polyorganosilane obtained by the method of the present invention is useful as an organic conductive material, a non-linear optical material, a photolytic reaction initiator, a precursor of silicon carbide ceramics, a photoresist material and the like, and intermediates thereof. Is.

[0035]

EXAMPLES The present invention will be described in more detail below with reference to examples. These examples do not limit the scope of the invention. In the following examples, parts represent parts by weight, and the following abbreviations are used. Me: Methyl group; Et: Ethyl group; Vi: Vinyl group; P
h: phenyl group

Example 1 Under an atmosphere of dry argon gas, 1,000 parts of hexamethylphosphoric triamide and 68 parts of sodium ethylate were placed in an eggplant-shaped flask equipped with a cooling tube and a Y-shaped tube, and the mixture was stirred at room temperature. 1,1,2,2-tetramethyl-1,2-diethoxydisilane (purity 90%, 1,
280 parts of 10% 1,2-trimethyl-1,2,2-triethoxydisilane) was added dropwise. 6 at room temperature
After stirring for a period of time, the reaction mixture was subjected to gas chromatography (filler: SE30). As a result, the starting disilane compound disappeared and dimethyldiethoxysilane and some methyltriethoxysilane peaks were observed. While stirring this at room temperature, dimethylvinylchlorosilane 10
0 part was dropped slowly. After stirring for 1 hour,
From the obtained mixture, sodium chloride produced by the desalting reaction and unreacted sodium ethylate were separated by filtration, and the low-boiling-point component was distilled off under the condition of 150 ° C./3 Torr. An organosilane was obtained.

¹ H NMR (CDC of the obtained polysilane
l ₃ , δ) was measured and found to be −0.5 to 0.4 (b
r. s, 9H, SiMe), 0.96 (t, J = 7H
z, 3H, SiOEt), 3.56 (q, J = 7 Hz,
2H, SiOEt) and 5.32 (m, 3H, SiV
A signal was observed in i). From this, it was confirmed that the vinyl group was introduced into the polysilane. The vinyl group-containing polyorganosilane obtained was subjected to gel permeation chromatography to obtain a weight average molecular weight (M
w) is 1,550, number average molecular weight (Mn) is 1,430
(Both converted to polystyrene).

Example 2 In the same manner as in Example 1, 200 parts of hexamethylphosphoric triamide, 10 parts of sodium ethylate, 1,
When the reaction was carried out using 40 parts of 1,2-trimethyl-1,2,2-triethoxydisilane and 20 parts of dimethylvinylchlorosilane, 4 parts of a vinyl group-containing polyorganosilane was obtained.

¹ H NMR (CDC of the obtained polysilane
l ₃ , δ) was measured and found to be −0.5 to 0.4 (b
r. s, 9H, SiMe), 0.96 (t, J = 7H
z, 3H, SiOEt), 3.56 (q, J = 7 Hz,
2H, SiOEt) and 5.32 (m, 3H, SiV
A signal was observed in i). From this, it was confirmed that the vinyl group was introduced into the polysilane. The vinyl group-containing polyorganosilane obtained was subjected to gel permeation chromatography to obtain a weight average molecular weight (M
w) is 3,160, number average molecular weight (Mn) is 2,950
(Both converted to polystyrene).

Example 3 Observation Under an argon gas stream, 20 parts of metallic sodium was charged into an eggplant-shaped flask equipped with a cooling tube and a Y-shaped tube, and 100 parts of n-hexane was added thereto. To this, 100 parts of dry ethanol was added to generate sodium ethylate. After the sodium had completely disappeared, n-hexane and excess ethanol were distilled off under reduced pressure. The reaction system was again made to flow under a dry argon gas stream, and tetrahydrofuran 50
Charge 0 part and stir at room temperature while stirring 1,1,2,2-
Tetramethyl-1,2-diethoxydisilane (purity 90
%, 1,1,2-trimethyl-1,2,2-triethoxydisilane (containing 10%)) was added dropwise. When the reaction mixture was subjected to gas chromatography (filler: SE30), the peak of the raw material disilane compound disappeared, and the peaks of dimethyldiethoxysilane and some methyltriethoxysilane were observed. Dimethyl (p-vinylphenyl) chlorosilane 1 while stirring at room temperature
00 parts was slowly added dropwise. From the obtained mixture, sodium chloride produced by the desalting reaction and unreacted sodium ethylate were filtered off, and further 100 ° C / 1To
When the low boiling point was distilled off under the condition of rr, 10 parts of polyorganosilane containing p-vinylphenyl group was obtained.

¹ H NMR (CDC of the obtained polysilane
l ₃ , δ) was measured and found to be −0.1 to 0.5 (m,
12H, SiMe), 0.96 (t, J = 7Hz, 3
H, SiOEt), 3.56 (q, J = 7Hz, 2H,
SiOEt), 6.0-6.7 (m, 3H) and 7.
_{2~7.8 (m, 4H, C 6} H 4 Vi) signal was observed. From this, the p-vinylphenyl group in polysilane was confirmed. When the obtained p-vinylphenyl group-containing polyorganosilane was analyzed by gel permeation chromatography, the weight average molecular weight (Mw) was 1,080 and the number average molecular weight (Mn) was 950 (both calculated as polystyrene). Met.

Example 4 In the same manner as in Example 1, 50 parts of tetrahydrofuran, 50 parts of sodium ethylate, 1,2-dimethyl-1,
When the reaction was carried out using 200 parts of 1,2,2-tetraethoxydisilane and 100 parts of dimethylvinylchlorosilane, respectively, 10 parts of a vinyl group-containing polyorganosilane was obtained.

¹ H NMR (CDC of the obtained polysilane
l _3, δ) was measured, -0.1~0.5 (b
r. s, 9H, SiMe), 1.20 (t, J = 7H
z, 3H, SiOEt), 3.86 (q, J = 7Hz,
2H, SiOEt) and 6.02 (m, 3H, SiV
A signal was observed in i). From this, a vinyl group in polysilane was confirmed. The vinyl group-containing polyorganosilane obtained was analyzed by gel permeation chromatography to find that the weight average molecular weight (Mw) was 5,400 and the number average molecular weight (Mn) was 4,150 (both calculated as polystyrene). there were.

Example 5 In the same manner as in Example 1, 500 parts of hexamethylphosphoric triamide, 68 parts of sodium ethylate, 1,
1,2,2-Tetramethyl-1,2-diethoxydisilane (purity 90%, 1,1,2-trimethyl-1,2,2
The reaction was carried out using 180 parts of triethoxydisilane (containing 10%) and 100 parts of dimethylphenylchlorosilane, and 10 parts of polyorganosilane containing a phenyl group was obtained.

¹ H NMR (CDC of the obtained polysilane
l ₃ , δ) was measured and found to be −0.1 to 0.5 (b
r. s, 9H, SiMe), 1.36 (t, J = 7H
z, 3H, SiOEt), 3.96 (q, J = 7 Hz,
2H, SiOEt) and 7.2-7.9 (m, 10
H, SiPh) signal was observed. From this, it was confirmed that the phenyl group was introduced into the polysilane. When the obtained phenyl group-containing polyorganosilane is analyzed by gel permeation chromatography,
Weight average molecular weight (Mw) is 1,000, number average molecular weight (M
n) was 850 (both converted to polystyrene).

Example 6 Under a dry argon gas stream, 100 parts of sodium ethylate and 500 parts of hexamethylphosphoric triamide were placed in a round-bottomed flask equipped with a cooling tube and a Y-shaped tube and stirred at room temperature. In addition to this, 1,1,2,2-tetramethyl-
300 parts of 1,2-diethoxydisilane was added dropwise. This was stirred at room temperature for 6 hours. When gas chromatography (filler: SE30) of the reaction mixture was measured, the peak of the starting disilane compound disappeared and the peak of dimethyldiethoxysilane was observed. To this, 100 parts of dimethylmethoxychlorosilane was slowly added dropwise at room temperature. After aging, the unreacted catalyst and chlorosilane were removed by filtration and vacuum distillation, and reprecipitation was performed with ethanol to obtain 30 parts of polyorganosilane.

¹ H NMR (CDC of the obtained polysilane
When l ₃ , δ) was measured, it was −0.2 to 0.3 (b
r. s, 10H, SiMe), 1.10 (t, J = 7H
z, 4H, SiOEt), 3.30 (s, 1H, SiO
Me) and 3.60 (q, J = 7 Hz, 3H, SiO
A signal was observed at Et). Moreover, when the obtained polysilane was analyzed by gel permeation chromatography, the weight average molecular weight (Mw) = 1,100, Mw
/Mn=1.15 (both converted to polystyrene). Thus, the ratio of the number of substituents of the obtained polymer is O.
A polysilane was obtained such that Me: OEt: Me = 1: 4: 10.

Claims (1)

[Claims] 1. A general formula: R ¹ _n Si ₂ (OR ² ) _6-n
(I) (In the formula, R ¹ and R ² each represent the same or different substituted or unsubstituted monovalent hydrocarbon group, and n is 0
A disilane compound represented by the formula: MOR ³ (II) (wherein R ³ represents a substituted or unsubstituted monovalent hydrocarbon group, and M represents an alkali metal). And reacting in the presence of an alkali metal hydrocarbinolate for a time sufficient to form a polyorganosilane; the reaction product system is then added to the general formula: R ⁴ _m SiX _4-m (III) ( In the formula, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrocarbyloxy group; X represents the same or different halogen atom, and m represents an integer of 1 to 3) A method for producing a polyorganosilane having an R ⁴ —Si group, which comprises reacting the indicated organohalosilane.