JP2758106B2 - Method for producing polyorganosilane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing polyorganosilane. More specifically, the present invention relates to a method for easily and safely producing polyorganosilane.

[0002]

2. Description of the Related Art Polyorganosilane is an organic conductive material,
It is known that it is useful as a nonlinear optical material, a photodecomposition type initiator, a silicon carbide precursor, a photoresist material and the like (for example, Miller, RD; Michil, J., Chem.
Rev., 89, 1359 (1989)).

A method for producing polyorganosilane includes the following:
The Wurtz process using organohalosilane or organohalodisilane as a starting material is widely used. However, the wurtz method involves dangers due to the use of metallic sodium and metallic potassium which are self-igniting in air, and the reaction conditions are severe, making it difficult to introduce substituents other than alkyl and aryl groups. There is a disadvantage that there is.

Some attempts have been made to solve such disadvantages. For example, Nagai et al. Did not use metal sodium or metal potassium, but in the presence of sodium alkoxide by a disproportionation reaction of 1,2-dialkoxytetramethyldisilanes to obtain dodecamethylcyclohexasilane and α, ω-disilane. Alkoxy oligosilanes have been obtained (JP-A-54-24874, JP-A-57
-146790).

Japanese Patent Application Laid-Open No. 62-62821 discloses a polyorganosilane obtained by disproportionating trimethyltrimethoxydisilane or a mixture of the disilane and dimethyltetramethoxydisilane in the presence of an alkali metal alcoholate. A production method is disclosed.

Further, Watanabe et al. (MeO) _n Me _6-n Si
₂ Polymethylmethoxysilane having an average molecular weight of 56,000 to 84,000 is synthesized by the disproportionation reaction of Me (representing a methyl group) (The 61st Annual Meeting of the Chemical Society of Japan (1991)) .

The disproportionation reaction using these alkoxydisilane compounds is excellent in that the reaction can be carried out under mild conditions without using metal sodium or metal potassium, but polysilane obtained by such a reaction is excellent. Are known only to contain a simple group such as a methyl group or a methoxy group as a substituent. However, considering the use of organopolysilanes for nonlinear optical materials and photoresists, it is desired to easily synthesize polysilanes having various substituents.

[0008] Such polysilanes having various substituents may be obtained by introducing a desired substituent into the starting disilane and performing a disproportionation reaction. However, to obtain such a disilane compound, it is difficult to selectively introduce a substituent by the reaction of several halogen atoms or alkoxy groups present in the disilane, or the boiling point of the generated disilane is high, There is a problem that distillation purification is difficult.

On the other hand, monosilane compounds having various organic groups are easier to synthesize than the corresponding disilane compounds,
Since the boiling point is relatively low, purification is easy. However, there is no known method for safely and easily obtaining polysilane from such a monosilane compound.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to convert polyorganosilanes having various substituents which can be easily used as the above-mentioned materials into disilane compounds and hydrocarbyloxysilanes which are easily available. An object of the present invention is to provide a method for safely producing a compound from a compound in one convenient step.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies on such problems and as a result, have simultaneously used a disilane compound and a hydrocarbyloxysilane compound .
The present inventors have found that the problem can be solved by performing a disproportionation reaction in the presence of an alkali metal hydrocarbinolate , and have completed the present invention.

That is, the present invention relates to a compound represented by the general formula: R ¹ _n Si ₂ (OR ² ) _6-n (I) wherein R ¹ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon. R ² represents a monovalent hydrocarbon group which is the same or different from each other, and n represents an integer of 0 to 6], and a general formula: R ³ _m Si (OR ⁴ ) _4-m (II) wherein R ³ represents a substituted or unsubstituted monovalent hydrocarbon group which is the same or different from each other, and R ⁴ represents a monovalent hydrocarbon group which is the same or different from each other , m represents an integer of 1 to 3, hydrocarbyl Oki represented by a n + m ≦ 8]
The Shishiran compounds of the general formula: MOR ⁵ (III) [wherein, M represents an alkali metal, R ⁵ represents a monovalent hydrocarbon radical alkali metal hydrocarbyl Nora represented by
And wherein the reaction is carried out in the presence of over preparative, wherein, R ^3, m is as described above] R ³ _m Si group in the molecular chain process for the preparation of polyorganosiloxane having.

In the disilane compound (I) used as one starting material in the present invention, examples of the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom represented by R ¹ include methyl, ethyl, Propyl, butyl,
Linear or branched alkyl groups such as pentyl, hexyl, octyl, decyl, dodecyl, and octadecyl; cycloalkyl groups such as cyclohexyl;
Aralkyl groups such as phenylethyl, 2-phenylpropyl and 3-phenylpropyl; aryl groups such as phenyl, tolyl and mesityl; alkenyl groups such as vinyl and allyl; p-vinylphenyl and p- (2-propenyl) phenyl Alkenylaryl groups; arylalkenyl groups such as styryl; and various substituted hydrocarbon groups such as halogenated hydrocarbon groups such as chloropropyl, chlorophenyl and 3,3,3-trifluoropropyl, and p-methoxyphenyl groups. You. These may be identical or different. A methyl group is particularly preferred because of ease of synthesis.

R ² is a silicon-functional group, hydrocarby
A monovalent hydrocarbon group that constitutes a hydroxy group; an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; a cycloalkyl group such as cyclohexyl; an aryl group such as phenyl and tolyl Alkenyl groups such as allyl and the like, and methyl, ethyl, n-propyl,
Alkyl groups such as isopropyl and phenyl groups are preferred, and methyl or ethyl are more preferred.

Specific examples of such a disilane compound (I) include hexamethyldisilane, 1,1,2,2-tetramethyl-1,2-diphenyldisilane, 1,2-dimethyl-1,1,1,2. , 2-tetraphenyldisilane, hexaphenyldisilane, 1,1,1-trimethyl-2,
2,2-triphenyldisilane, 1,2-dimethyl-
Hexaorganodisilane compounds such as 1,2-diphenyl-1,2-divinyldisilane; pentamethylmethoxydisilane, pentaethylmethoxydisilane, 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-te
rt-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-1,1,2-triphenyl-2
Monomethoxydisilane compounds such as -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-dimethoxydisilane, 1,
1,2-dimethoxydisilane compounds such as 1-dimethyl-2,2-diphenyl-1,2-dimethoxydisilane; 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-tetraphenyl-2,2-
1,1-dimethoxydisilane compounds such as 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-
1,1,2-trimethoxydisilane compounds such as 1,1,2-trimethoxydisilane and 1,1,2-triphenyl-1,2,2-trimethoxydisilane; 1,1,1
-Trimethyl-2,2,2-trimethoxydisilane,
1,1-dimethyl-1-phenyl-2,2,2-trimethoxydilan, 1-methyl-1,1-diphenyl-2,
1, such as 2,2-trimethoxydisilane, 1,1,1-triphenyl-2,2,2-trimethoxydisilane
1,1-trimethoxydisilane compound; 1,2-dimethyl-1,1,2,2-tetramethoxydisilane, 1-methyl-2-phenyl-1,1,2,2-tetramethoxydisilane, 1,2 1,1,2,2-tetramethoxydisilane compounds such as diphenyl-1,1,2,2-tetramethoxydisilane; 1,1-dimethyl-1,2,2
2,2-tetramethoxydisilane, 1-methyl-1-phenyl-1,2,2,2-tetramethoxydisilane,
1,1,1,2-tetramethoxydisilane compounds such as 1,1-diphenyl-1,2,2,2-tetramethoxydisilane; pentamethoxydisilane compounds such as methylpentamethoxydisilane and phenylpentamethoxydisilane; Hexamethoxydisilane; and some or all of the methoxy groups of these compounds are ethoxy, n-
And those substituted with other carbyloxy groups such as propoxy, isopropoxy, and phenoxy.

Such a disilane compound (I) can be obtained by hydrocarbyloxylation , for example, alkoxylation or aryloxylation of a halogenated disilane compound;
Introduction of alkyl groups and other organic groups into the viroxylated disilane compound; chlorination of the alkyl or aryl disilane compound followed by hydrocarbyl oxylation,
For example, it can be synthesized by a known method such as alkoxylation or aryloxylation. For example, Experimental Chemistry Course 1
Volume 2, Organometallic Compounds (Maruzen), Third Edition, Chapter 16, Chapter 3
The reaction described in detail on pages 31 to 377 may be used. 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 hydrocarbyloxysilane compound (II) used as another starting material in the present invention, the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom represented by R ³ includes the above-mentioned monovalent hydrocarbon groups. Those exemplified for R ¹ can be mentioned. Hydrocarbyloxysi
Run compounds are those having a variety of R ³ is, R ¹ in the corresponding disilane compound having the same groups as R ¹
Than the introduction of not only relatively easy to introduce the R ^3, since boiling point generally lower than the above corresponding disilane compounds, even those R ³ is thermally unstable manner can be easily purified. Therefore, the preferred range of R ³ is, depending on the intended use of the polyorganosilane, methyl, ethyl, tert-butyl, n-hexyl, phenyl, p-tolyl, vinyl, p-vinylphenyl, styryl and 3, Various things, such as 3,3-trifluoropropyl, are mentioned. In the case of a hydrocarbyloxysilane compound in which a plurality of R ³ are bonded to the same silicon atom, they may be the same or different.

R ⁴ is a monovalent hydrocarbon group constituting a hydrocarbyloxy group, and examples thereof include those described above for R ² . Because of the ease of synthesis and reactivity, methyl,
Alkyl groups such as ethyl, n-propyl and isopropyl and phenyl groups are preferred, and methyl or ethyl is more preferred.

Such hydrocarbyloxysilanation
Specific examples of compound (II) include trimethylmethoxysilane, triethylmethoxysilane, trivinylmethoxysilane, tripropylmethoxysilane, triphenylmethoxysilane, methyldiphenylmethoxysilane, dimethylphenylmethoxysilane, dimethylvinylmethoxysilane, and dimethyl ( p-vinylphenyl) methoxysilane, dimethylstyrylmethoxysilane, dimethyl-n-
Monomethoxysilane compounds such as hexylmethoxysilane and methylvinylphenylmethoxysilane; dimethyldimethoxysilane, methylphenyldimethoxysilane,
Dimethoxysilane compounds such as diphenyldimethoxysilane, methyl-n-hexyldimethoxysilane, methyl-tert-butyldimethoxysilane, methylvinyldimethoxysilane, divinyldimethoxysilane, methyl (p-vinylphenyl) dimethoxysilane, methylstyryldimethoxysilane; Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, n-hexyltrimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, (p-vinylphenyl) Trimethoxysilane compounds such as trimethoxysilane and styryltrimethoxysilane; and some or all of the methoxy groups of these compounds are ethoxy, n- Propoxy, isopropoxy,
Examples include those substituted with another hydrocarbyloxy group such as phenoxy.

Such a hydrocarbyloxysilanation
Compound (II), the ratio of organochlorosilanes obtained by direct synthesis from metallic silicon and monochloro hydrocarbon
It can be synthesized by drocarbyl oxylation , for example, by alkoxylation or aryloxylation. Alternatively, a known method such as a Grignard reaction of a halosilane, a hydrosilylation reaction of a silane having a Si—H bond, or a reaction of an organic chloride with a halosilane in the presence of aluminum chloride is used to introduce a desired R ^3. be able to. Further, in order to obtain a hydrocarbyloxysilane compound having a desired number of hydrocarbyloxy groups , a disproportionation reaction in the presence of a Lewis acid or the like can be used.

Disilane compound (I) or hydrocarbyl compound
The number of hydrocarbyloxy groups in the xysilane compound (II) is selected according to the molecular structure and molecular weight of the target polyorganosilane. For example, monohydrocal
Biloxydisilane or 1,2-bishydrocarb
Leoxysidisilane and monohydrocarbyloxysila
When a disproportionation reaction is carried out in combination with styrene or bishydrocarbyloxysilane , a chain or cyclic polyorganosilane is obtained. Of these, monohydrocarbyl
Reacting with oxydisilane and monohydrocarbyloxysilane yields relatively low molecular weight polyorganosilanes. In addition two or more fire to the same silicon atom
Disilane compounds having a drocarbyloxy group and tris
If hydrocarbyloxysilane is used as a raw material, a branched or reticulated polyorganosilane can be obtained.

However, in the disproportionation reaction between the disilane compound having no hydrocarbyloxy group and the monohydrocarbyloxysilane , only another disilane compound is formed, and a trisilane compound or a polysilane higher than that cannot be obtained. From this, in the above general formula, n
+ M ≦ 8 is required.

Further, in some cases, two or more disilane compounds and / or hydrocarbyl ox
By using a silane compound as a raw material, it is possible to synthesize a polyorganosilane having any combination of various substituents.

The disilane compound (I) used and hydrocarb
The amount ratio of the viroxysilane compound (II) is not particularly limited, but is preferably 0.5 or more, more preferably 1 or more in a molar ratio of (I) / (II).

Alkali gold used as a catalyst in the present invention
In the genus hydrocarbinolate (III), examples of the alkali metal represented by M include lithium, sodium, potassium, rubidium and cesium, and lithium, sodium and potassium are preferable in terms of availability. As the monovalent hydrocarbon group represented by R ⁵ , those similar to R ² can be exemplified, and methyl, ethyl, te
Lower alkyl groups such as rt-butyl are preferred.

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

The amount of the alkali metal hydrocarbinolate is not particularly limited, and can be used in an amount of 0.01 to 50 mol% based on the disilane compound (I) used. If the amount of the catalyst is too small, the reaction becomes very slow. If the amount is too large, not only is it difficult to remove the catalyst after the reaction, but also it is economically disadvantageous. The amount of the catalyst is preferably 0.1 to 30 mol% based on the disilane compound (I).

In the reaction, for example, a difunctional disilane compound and a diorganobishydrocarbyl ox
When a silane compound is used, it proceeds as in the following formula,
Form polyorganosilane.

[0029]

Embedded image

[In the formula, R ^{1 to} R ⁵ and M are as described above, x and y represent the number of moles of the disilane compound and the hydrocarbyloxy compound, respectively, which participated in the reaction, and R represents R ² , R ⁴ or R ^5. ]

In the reaction, the raw material disilane compound (I) or hydrocarbyloxysilane compound (II) is dissolved, and the catalyst is an alkali metal hydrocarbinolate.
A reaction solvent can be used, if necessary, to disperse (III) effectively, smoothly carry out the reaction and control the reaction temperature, or to improve the catalytic activity. Such solvents include toluene, xylene, n
Hydrocarbon solvents such as hexane, n-heptane and cyclohexane; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; dimethylformamide, dimethyl sulfoxide ,
An aprotic polar active medium such as hexamethylphosphoric triamide is exemplified.

The production method of the present invention comprises the steps of: starting material disilane compound (I), hydrocarbyloxysilane compound (II),
Since both by-product hydrocarbyloxysilanes and the catalyst are easily decomposed by reaction with water, the reaction is performed in a substantially anhydrous state. That is, the reaction is carried out by mixing a disilane compound, a hydrocarbyloxysilane compound and a catalyst, and, if necessary, a solvent previously dried by an ordinary method in a dried inert gas.

The reaction is usually carried out at a temperature in the range of -80 to 250 ° C, preferably 20 to 180 ° C. Raw material disilane compound, hydrocarbyloxysilane compound , solvent used and hydrocarbyloxysila by-produced by the reaction
The reaction temperature can be determined by the relationship of the boiling points of the compound . Also, the disilane compound or hydrocarbyl used
Depending on the type of the oxysilane compound, an alkoxysilane having a relatively low boiling point may be by-produced by the reaction. In this case, in order to keep the reaction temperature high, using a reaction condition lower than the boiling point of the hydrocarbyloxysilane compound used as a raw material and higher than the boiling point of the low-boiling alkoxysilanes produced as by-products, The reaction may be performed while distilling off.

The reaction is preferably carried out at ambient atmospheric pressure. However, higher or lower pressures can be applied if desired.

The polyorganosilane obtained by the reaction may be added in excess or in the form of hydrocarbyl formed.
Alkali metal hydrocarbyls as oxysilane compounds and catalysts
Isolated by removing the nolate . If necessary, purification can be performed by reprecipitation, distillation, column chromatography, or the like.

[0036]

According to the present invention, the disilane compound used as a raw material has one or more R
¹ and, by hydrocarbyloxy silane compound arbitrarily selected one or more of the R ³ having in the molecule can be synthesized polyorganosiloxane having any organic groups bonded to the silicon atom . In particular, the disilane compound is difficult to synthesize easily and in good yield, and / or has a high boiling point but is difficult to purify due to its thermal instability. Organic groups that are difficult to introduce
Via a hydrocarbyloxysilane compound as R ³ ,
It can be safely and easily introduced.

According to the method of the present invention, a wide range of substituted or unsubstituted ones bonded to a silicon atom, such as a phenyl group, a vinyl group, a p-vinylphenyl group, a styryl group and a trifluoropropyl group, as well as a methyl group. It is possible to safely produce a polyorganosilane having a chain or other silicon-silicon skeleton having a valent hydrocarbon group and containing no group unstable to hydrolysis.
The polyorganosilane obtained by the method of the present invention is useful as an organic conductive material, a nonlinear optical material, a photodecomposition type reaction initiator, a precursor of a silicon carbide ceramic, a photoresist material, and the like.

Further, the hydrocarb obtained by the present invention
Polyorganosilanes having a viroxy group , particularly an alkoxy group, in the molecule can be further increased in molecular weight.

[0039]

The present invention will be described in more detail with reference to the following examples. These examples do not limit the scope of the invention. In the following examples, “parts” means “parts by weight”, and the following abbreviations are used in addition to the aforementioned Me (methyl group). Et: ethyl group; Vi: vinyl group; Ph: phenyl group

Example 1 Under a dry argon gas flow, a cooling pipe and a rubber stopper
In a one-necked flask, 1,1,2,2-tetramethyl-1,
103 parts of 2-diethoxydisilane, 136 parts of diphenyldiethoxysilane, 3.4 parts of sodium ethylate and 10 parts of hexamethylphosphoric triamide were charged and reacted at 80 ° C. for 6 hours with stirring. After the reaction,
When the gas chromatograph (filler SE30) of the mixture was measured, the peak of the raw material disilane compound disappeared, and the peak of dimethyldiethoxysilane was observed. The sodium ethylate was filtered off from the obtained mixture, and further filtered for 15 minutes.
The low boiling point was distilled off at 0 ° C / 1 Torr.
Parts of polysilane were obtained.

¹ H NMR (CD) of the obtained polysilane
Cl ₃ , δ) was measured to be 0.1 to 0.5 (m,
6H), 1.33 (t, J = 7 Hz, 3H), 4.03
(Q, J = 7 Hz, 2H) and 7.2 to 8.1 (m, 1
At 0H), a signal was observed. When the obtained polysilane was analyzed by gel permeation chromatography, the weight average molecular weight (Mw) was 596, and the number average molecular weight (Mn) was 558 (both in terms of polystyrene). From these data, the obtained polysilane has the average composition formula: (EtO) (Me ₂ Si) ₂ (Ph ₂ Si)
₂ (OEt).

Example 2 The same amounts of the reactants, catalyst and solvent as used in Example 1 were charged into a two-necked flask equipped with a simple distillation system and a rubber stopper under a stream of dry argon gas to produce the flask. The reaction was carried out at 140 ° C. for 6 hours while distilling off dimethyldiethoxysilane. After the reaction, the mixture was measured by gas chromatography (filler SE30), and it was observed that the peak of the raw material disilane compound had disappeared. The sodium ethylate was filtered off from this mixture, and further filtered at 150 ° C./1
When the low-boiling components were distilled off under rr conditions, 19.5 parts of polysilane was obtained.

¹ H NMR (CD) of the obtained polysilane
Cl ₃ , δ) was measured to be 0.1 to 0.5 (m,
6H), 1.33 (t, J = 7 Hz, 3H), 4.03
(Q, J = 7 Hz, 2H), 7.2 to 8.1 (m, 25
A signal was observed at H). When the obtained polysilane was analyzed by gel permeation chromatography, the weight average molecular weight (Mw) was 1,020 and the number average molecular weight (Mn) was 870. From these data,
The obtained polysilane has an average composition formula: (EtO) (Me
₂ Si) ₂ (Ph ₂ Si) ₅ (OEt).

Example 3 In the same apparatus as used in Example 1, 103 parts of 1,1,2,2-tetramethyl-1,2-diethoxydisilane, 80 parts of methylvinyldiethoxysilane, sodium ethylate 3.4 parts and 10 parts of hexamethylphosphoric triamide were charged and reacted at 80 ° C. for 6 hours with stirring. After the reaction, the mixture is subjected to gas chromatography (filler S
When E30) was measured, the peak of the raw material disilane compound disappeared, and the peak of dimethyldiethoxysilane was observed. In addition to these, (EtO) Me ₂ Si
A peak derived from (ViMeSi) _n (SiMe ₂ ) _m (OEt) was observed. The sodium ethylate was filtered off from this mixture, and the low-boiling components were distilled off at 150 ° C./1 Torr. As a result, 12.7 parts of polysilane was obtained.

¹ H NMR (CD) of the obtained polysilane
Cl ₃ , δ) was measured to be 0.1 to 0.5 (m,
18H), 1.33 (t, J = 7 Hz, 3H), 4.03
(Q, J = 7 Hz, 2H), 5.8-6.6 (m, 3H)
A signal was observed. When the obtained polysilane was analyzed by gel permeation chromatography, the weight average molecular weight (Mw) was 500 and the number average molecular weight (Mn) was 460. As a result, the obtained polysilane had an average composition formula (EtO) (ViMeSi) ₂ (M
e ₂ Si) ₅ (OEt).

Example 4 A mixed methylethoxydisilane obtained by reacting a disilane fraction having a boiling range of 145 to 160 ° C. with anhydrous ethanol by-produced during the direct synthesis of methylchlorosilanes from methyl chloride and metallic silicon. , As a disilane compound. This mixture was measured by gas chromatography and found to be Me ₄ (EtO) ₂ Si ₂ : Me ₃ (EtO) ₃ S
The chromatogram area ratio of i ₂ : Me ₂ (EtO) ₄ Si ₂ was 13:30:55.

In the same apparatus as used in Example 2, 100 parts of the above-mentioned disilane mixture, 136 parts of diphenyldiethoxysilane, 3.4 parts of sodium ethylate and 10 parts of hexamethylphosphoric triamide are charged and produced. The reaction was carried out at 140 ° C. for 12 hours while distilling off methyltriethoxysilane and dimethyldiethoxysilane. After the reaction, the mixture is subjected to gas chromatography (filler SE
30), it was observed that the peak of the raw material disilane compound disappeared. 150 ° C from this mixture
When low boiling components were distilled off under the condition of / 1 Torr, 18.2
Parts of polysilane were obtained.

Of the obtained polysilane¹H NMR (CD
Cl_Three , Δ) was measured to be 0.1 to 0.5 (m,
15H), 1.33 (t, J = 7 Hz, 3H), 4.03
(Q, J = 7 Hz, 2H), 7.2 to 8.1 (m, 8H)
A signal was observed. In addition, the obtained polysilane
Analyze by gel permeation chromatography
And weight average molecular weight (Mw) = 1,500, number average molecule
The amount (Mn) was 1,100. As a result,
Polysilane has an average composition formula (MeSi)₈ (Me _Two S
i)₆ (Ph_Two Si)_Three (OEt)_Four Turned out to be
did.

Example 5 In the same apparatus used in Example 2, 100 parts of the same disilane mixture as used in Example 4, 98 parts of phenyltriethoxysilane, 3.4 parts of sodium ethylate and hexamethylphos 10 parts of holic triamide was charged and reacted at 140 ° C. for 12 hours while distilling off methyltriethoxysilane and dimethyldiethoxysilane formed. After the reaction, the mixture was measured by gas chromatography (filler SE30), and it was observed that the peak of the raw material disilane compound had disappeared. The sodium ethylate was separated from this mixture by filtration, and the low-boiling component was distilled off under the conditions of 150 ° C./1 Torr. As a result, 20 parts of polysilane was obtained.

¹ H NMR (CD) of the obtained polysilane
Cl ₃ , δ) was measured to be 0.1 to 0.5 (m,
10H), 1.33 (t, J = 7 Hz, 3H), 4.03
(Q, J = 7 Hz, 2H), 7.2 to 8.1 (m, 3H)
A signal was observed. Further, when the obtained polysilane was analyzed by gel permeation chromatography, it was found that the weight average molecular weight (Mw) was 1,150 and the number average molecular weight (Mn) was 970. As a result, the obtained polysilane had an average composition formula (MeSi) ₆ (Me ₂ Si) ₅
(Ph ₂ Si) ₅ (OEt) ₃ was found to be present.

Example 6 The same apparatus as used in Example 1 was replaced with 1,1,2,2-te
206 parts of tramethyl-1,2-diethoxydisilane , dimethyl (p-vinylphenyl) ethoxysilane 103
, 3.4 parts of sodium ethylate and 1,034 parts of 1,4-dioxane, and stirred at 80 ° C for 6 hours.
Allowed to react for hours. After the reaction, the obtained mixture was measured by gas chromatography (filler SE30). As a result, the peak of the raw material disilane compound disappeared, and the peak of dimethyldiethoxysilane was observed. The sodium ethylate was filtered off from this mixture, and the low-boiling components were distilled off at 150 ° C./1 Torr to obtain 12.0 parts of polysilane.

The obtained polysilane was analyzed by ¹ H NMR (CD
Cl ₃ , δ) was measured to be 0.1 to 0.5 (m,
12H), 6.0-6.7 (m, 3H), 7.2-7.
A signal was observed at 8 (m, 4H). When the obtained polysilane was analyzed by gel permeation chromatography, the weight average molecular weight (Mw) was 600.
Met. As a result, it was found that the molecular structure of the obtained polysilane was represented by the following average composition formula.

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──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 77/60

Claims (1)

(57) [Claims] 1. A general formula: R ¹ _n Si ₂ (OR ² ) _6-n (I) wherein R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group which is the same or different from each other, R ² represents a monovalent hydrocarbon group which is the same or different from each other, and n represents an integer of 0 to 6], and a general formula: R ³ _m Si (OR ⁴ ) _4-m ( II) wherein R ³ represents a substituted or unsubstituted monovalent hydrocarbon group which is the same or different from each other, R ⁴ represents a monovalent hydrocarbon group which is the same or different from each other, and m represents 1 represents -3 integer, hydrocarbyl Oki represented by a n + m ≦ 8]
The Shishiran compounds of the general formula: MOR ⁵ (III) [wherein, M represents an alkali metal, R ⁵ represents a monovalent hydrocarbon radical alkali metal hydrocarbyl Nora represented by
A method for producing a polyorganosilane having an R ³ _m Si group in the molecular chain (where R ³ and m are as described above), characterized in that the reaction is carried out in the presence of a salt.