JPH0424366B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention is based on the general formula () (In the formula, R represents a hydroxyl group, an amino group, a vinyl group, a lower alkyl group, a lower alkoxy group, or a halogen atom.) 1,2,2-trimethyl-1-(substituted phenyl)polydisilane ( Invention related to polysilane (hereinafter referred to as polysilane ()) and the general formula () which is the raw material 1,2-dichloro-1,2,2-trimethyl-
The present invention relates to a method for producing polysilane (), which comprises subjecting 1-substituted phenyldisilane (hereinafter referred to as disilane ()) to a condensation reaction in the presence of an alkali metal or alkaline earth metal. The polysilane () of the present invention is a useful compound having a function as an electronic material such as a photoresist material, an organic semiconductor, an optical information storage material, or a preceramic, and is a novel compound that has not been described in any literature. (Prior art) Conventionally, as a method for producing polysilanes, the general formula () (wherein, X is an alkyl group or an aryl group,
represents a positive integer) [The Journal of American
Chemical Society, 71 , 963 (1949),
Chemistry Letters, 1976 , 551 (1976) and
Journal of Polymer Science：Polymer
Letters Edition, 21 , 819 (1983)] or general formula () (In the formula, X has the same meaning as above, Y represents an alkyl group or an aryl group, and n and m represent positive integers.) Method for producing a copolymer of dimethylpolysilane and arylalkylpolysilane [US patent No. 4260780 and Journal of Polymer
Science: Polymer Chemistry Edicion, 22 ,
159 (1984)] is on display. (Problems to be Solved by the Invention) Conventional polysilanes are homopolymers in which alkyl groups and aryl groups are introduced into the main chain consisting of silicon-silicon bonds, or general polysilanes, as shown in the general formula () above. As shown in formula (), it is only a polysilane such as a copolymer in which dimethylsilane units and arylalkylsilane units are irregularly polymerized, and as in the present invention, a methyl group is added to the main chain consisting of silicon-silicon bonds as a substituent. However, no polysilane in which substituted phenyl groups are introduced regularly has been found. (Means for Solving the Problems) The present inventors have developed a method for producing polysilane in which methyl groups and substituted phenyl groups are regularly introduced as substituents into the main chain consisting of silicon-silicon bonds.
General formula () (wherein R' represents the same meaning as above) is used as a raw material, and by subjecting this disilane () to a condensation reaction in the presence of an alkali metal or alkaline earth metal, the general formula ( ) (In the formula, R represents the same meaning as above.) It was discovered that a polysilane () consisting of a repeating unit represented by the above formula can be obtained, and the present invention was completed. The method for producing polysilane () of the present invention involves condensing disilane () in an aprotic solvent such as n-pentane, n-hexane, benzene, toluene, tetrahydrofuran, etc. in the presence of an alkali metal or alkaline earth metal. let The alkali metals used in the present invention are preferably lithium, sodium, potassium, etc., and the alkaline earth metals are preferably magnesium, calcium, etc.
Particularly suitable are lithium, sodium, and potassium. In addition, the substituents of the substituted phenyl group of disilane (), which is the raw material of the present invention, are hydroxyl group, amino group, vinyl group, lower alkyl group, lower alkoxy group, and halogen atom. It may be protected, and a trialkylsilyl group is suitable as a protecting group, and a benzyl group and a tetrahydropyranyl group are also suitable as a protecting group for a hydroxyl group. In this reaction, a minimum of 2 alkali metals or alkaline earth metals are used per 1 equivalent of disilane ().
An equivalent amount is required, and usually 2 to 3 equivalents are used. The reaction temperature is 0°C or higher and lower than the boiling point of the reaction solvent. The reaction time varies depending on the type of alkali metal or alkaline earth metal used, the reaction solvent and the reaction temperature, but usually takes 1 to 50 hours. After the reaction is complete,
The reaction solvent is removed and, if necessary, the polysilane is purified by a conventional purification method for polysilanes, such as repeated reprecipitation with a benzene-alcohol system, to obtain polysilane (2). (Effects of the Invention) The present invention provides a main chain consisting of silicon-silicon bonds by carrying out a condensation reaction of disilane () in the presence of an alkali metal or an alkaline earth metal.
We have discovered a polysilane () in which methyl groups and substituted phenyl groups are regularly introduced as substituents. Polysilane obtained by the present invention ()
has a weight average molecular weight ( Mw ) of 5,000 to 500,000 and a degree of dispersion ( Mw / Mn ) of 2.0 to 30.0, and can function as electronic materials or preceramics such as photoresist materials, organic semiconductors, and optical information storage materials. have (Example) The present invention will be explained below with reference to Examples. Example 1 A four-necked flask equipped with a cooling tube, dropping funnel, thermometer, and stirrer was purged with argon, and then 300 g of toluene and 23 g (1 mol) of sodium were added.
and while stirring, add 1,2-dichloro-1,
A toluene solution of 131.6 g (0.5 mol) of 2,2-trimethyl-1-(4-methoxyphenyl)disilane was added dropwise over 1 hour while maintaining the reaction temperature at 50°C. After the dropwise addition was completed, the reaction was continued at 50°C for 20 hours. After the reaction is completed, the mixture is cooled to room temperature, the by-produced sodium salt is separated, and the liquid is concentrated to remove toluene. Add 300ml of benzene to the concentrated residue,
While stirring, 1 portion of ethanol was added to crystallize polysilane. The adhering solvent was completely removed under reduced pressure, and a white powder of 1,2,2-trimethyl-1-
49.1 g of (4-methoxyphenyl)polydisilane was obtained. Yield 51%. ^H1 -nuclear magnetic resonance spectrum (60MHz, _CDC3 ) δppm=-0.5~1.0 (broad, Si- _CH3 , 9H) 3.5-4.1 (broad, Ph- _OCH3 , 3H) 6.0-7.5 (broad, Si- Ph -, 4H) Gel permeation chromatography Measurement conditions: Column Hitachi Chemical GL-R400M Eluent Tetrahydrofuran Flow rate 1.0ml/min Weight average molecular weight (w) 97000 Dispersion degree (w/n) 6.5 Example 2~ 8 Using the disilane () listed in Table 1 as a raw material, the same procedure as in Example 1 was carried out to obtain the polysilane () listed in Table 1. The yield and analytical values are listed in Table 1.

[Table] Eluent Tetrahydrofuran
Flow rate 1.0ml〓〓

Claims (1)

[Claims] 1 General formula () (In the formula, R represents a hydroxyl group, an amino group, a vinyl group, a lower alkyl group, a lower alkoxy group, or a halogen atom) 1,2,2-trimethyl- 1-
(Substituted phenyl)polydisilane. 2 General formula () (In the formula, R′ is a hydroxyl group, an amino group, a vinyl group,
A 1,2-dichloro-1,2,2-trimethyl-1-substituted phenyldisilane represented by a lower alkyl group, a lower alkoxy group, a halogen atom, or a hydroxyl group or an amino group having a protective group is combined with an alkali metal or alkaline earth General formula () characterized by carrying out a condensation reaction in the presence of a similar metal (In the formula, R represents the same meaning as above), weight average molecular weight
5000-500000 1,2,2-trimethyl-1-
A method for producing (substituted phenyl)polydisilane.