JPH0341122A - Aryl-substituted polycarbosilane and its production - Google Patents

Abstract

PURPOSE:To produce the subject polymer composed of alternating Si-Si bonds and ethylene parts and having an aryl on the Si atom by reacting a specified disilylethane with an alkali metal. CONSTITUTION:A 1-silyl-2-silylethane of formula I [wherein R<1>-R<4> are each a (substituted) aryl or an alkyl and at least one of them is a (substituted) aryl; and X is Cl, Br or I] is reacted with an alkali metal to produce a polycarbosilane wherein the main chain is represented by formula II (wherein (n)>=3), and the substituents on the silicon atoms in each repeating unit of the main chain are a (substituted) aryl and an alkyl, and at least one of them is a (substituted) aryl. This polymer not only can be used as a material for silicon carbide ceramics but also has a possible use as a photoreactive polymer of, e.g. a resist in virtue of its sigma-pi conjugation between the Si-Si bond part and the aryl.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to poly(disilene-ethylene), which is a polycarbosilane in which disylene moieties and ethylene moieties are arranged alternately in the main chain and has an aryl group on silicon. and its manufacturing method. These polysilene-ethylene) compounds can be used as raw materials for silicon carbide ceramics, and due to the σ-π conjugation between the 5i-3i bond and the aryl group, they are expected to be used as photoreactive polymers such as resists.

[Prior art and its problems]

Conventionally, various types of polymers containing silicon atoms have been known, but poly(
Disilene-ethylene) have not been known so far.

[Problem of invention]

An object of the present invention is to provide poly(disilene-ethylene) having an aryl group on silicon and a method for producing the same.

[Means for Solving the Problems] As a result of intensive research to achieve the above-mentioned problems, the present inventors have discovered that 1-herosilyl-2-halosilylethanes having an aryl group on silicon can be combined with an alkali metal. It was discovered that poly(disilene-ethylene) having an aryl group on silicon can be obtained by the reaction, and the present invention was achieved.

Poly(disylene-ethylene) provided in the present invention
%() (where n represents an integer of 3 or more), and at least one of the substituents on silicon in each main chain repeating unit is One is an aryl group which may have a substituent, and the other is an alkyl group which may have a substituent. Examples of these aryl groups include phenyl, tolyl, trifluoromethylphenyl, phenylphenyl, and naphthyl groups. Examples of alkyl groups include methyl, ethyl, and propyl groups. Examples of the substituent include a trifluoromethyl group, an alkoxy group, and the like. Examples of the above poly(disilene-ethylene) are as follows.

Poly(trimethylphenyldisilene-ethylene), poly(dimethyldiphenyldisilene-ethylene), poly(trimethylnaphthyldisilene-ethylene), poly(methyltriphenyldisilene-ethylene), poly(tetraphenyldisilene-ethylene) etc.

In the method for producing the compound of the present invention, l-silyl-2-silylethanes used as raw materials have the general formula Represents a good aryl group or alkyl group, but R',
At least one of R', R'', and R'' is an aryl group that may have a substituent, and X represents chlorine, bromine, or iodine. be.

Examples of these aryl groups include phenyl group, tolyl group,
trifluoromethylphenyl group, phenylphenyl group,
Examples include naphthyl groups, and examples of alkyl groups include methyl groups, ethyl groups, and probylene groups! −(
chlorodimethylsilyl)-2-(chloromethylphenylsilyl)ethane, 1,2-bis(chloromethylphenylsilyl)ethane, l-(chlorodimethylsilyl)-2-
(chloromethylnaphthylsilyl)ethane, 1-(chlorodiethylsilyl)-2-(chloroethylphenylsilyl)ethane, 1-(chloromethylphenylsilyl)-2-
(chlorodiphenylsilyl)ethane, 1.2-bis(chlorodiphenylsilyl)ethane, 1.2-bis(bromomethylphenylsilyl)ethane, 1.2-bis(iodomethylphenylsilyl)ethane, and the like.

As the alkali metal used in the production method of the present invention, lithium, sodium, potassium, etc. can be used, and these can be used alone or as a mixture or alloy.

It is preferable that it be in the form of a dispersion or a liquid, but depending on the reaction conditions, it can also be used as a lump.

The molar ratio of the alkali metal to the 1-silyl-2-silylethanes is sufficient to be 2:1, but it can be selected to be a in the range of IO+1 to 221.

Although the production method of the present invention does not particularly require the use of a solvent,
When using a solvent, any solvent can be used as long as it does not react with the halosilanes and alkali metals. Examples of this include hexane, benzene, toluene, xylene, and ethylbenzene.

The method of the invention can be carried out at any temperature above room temperature. When a bulk alkali metal is used and the reaction is carried out at a temperature close to room temperature, it is desirable to activate the surface of the alkali metal by ultrasonic irradiation or the like. The produced polymer can be easily separated from the reaction mixture by solvent extraction after hydrolysis of the reaction solution.

[Effects of the Invention] The present invention provides poly(disilene-ethylene) having 5i-3i bonds and ethylene moieties alternately and having an aryl group on silicon, and its industrial significance is extremely large. .

〔Example〕

EXAMPLES The present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A solution of 5 mmol of 1-(chlorodimethylsilyl)-2-(chloromethylphenyl)ethane in toluene (5-) was added to 0.85 g of 40% sodium dispersion (light oil) heated to 80°C in toluene. (lomfl) was added dropwise to the slurry and heated at 80° C. for an additional 12 hours. After cooling, the mixture was decomposed with ethanol 2-1 and water 10-1, extracted with toluene, and the toluene phase was washed with water. The toluene phase was concentrated to dryness, dissolved in tetrahydrofuran, and reprecipitated by adding methanol to obtain 0.37 g of a pale brown gum-like substance. The substance obtained as described above has the formula: CH,C,H.

The molecular iMw of polystyrene equivalent by GPC method is 89,000, and its I
R and NMR spectral analysis are as follows.

[IR (KBr) analysis (wavelength mark -°)] TeS60 (m)
, 2910 (VS), 2850 (S), +485 (IR
), +460 (S), +425 (S), 1400 (m)
, 1375 (m), +295 (m), 1240 (vs
), +130 (vs), 1100 (vs), 105
0 (vs), 830 (s), 770 (s), 730 (s
), 695(s), 610(s), 465(s).

[NMR (THF-d, ) (ppm) analysis] 0.0
9-0.10(Sj(CH,), 6H,m), 0.
21-0.35(PhSiC1(,,3H,l11),
0.5-1.0 (CI-1, CH,, 4H, m), 7.
2-7,6(C,I(,,511,m).

Claims (2)

[Claims] (1) The main chain is represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Polycarbosilanes are an aryl group or an alkyl group that may have a substituent, and at least one of them is an aryl group that may have a substituent. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2, R^3, R^4 are aryl groups or alkyl groups that may have substituents Representation,
At least one of R^1, R^2, R^3, and R^4 is an aryl group that may have a substituent, and X represents chlorine, bromine, or iodine. Silyl-2-silylethanes are reacted with an alkali metal, and the main chain is represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where n represents an integer of 3 or more). The substituents on the silicon in each main chain repeating unit are an aryl group or an alkyl group which may have a substituent, but at least one is an aryl group which may have a substituent. A method for producing certain polycarbosilanes.