JPS6084330A - Production of high-molecular organosilicon compound - Google Patents

Abstract

PURPOSE:To produce the titled linear or branched high-molecular compound having a regular atomic arrangement and a controlled degree of polymerization, by reacting a Grignard reagent with a specified organosilicon compound in an organic solvent containing metallic Mg. CONSTITUTION:20mol or below, per mol of metallic Mg, of a Grignard reagent of formula I (wherein R<1> is an (un)substituted monovalent hydrocarbon group, a triorganosilalkyl or a silphenyl, and X is a halogen) and 0.9-1.1mol, per mol of metallic Mg, of an organosilicon compound of formula II (wherein R<2> is H or a monovalent hydrocarbon group, R<3> is a 1-6C bivalent hydrocarbon group, X is a halogen, and n is 1 or 2) are reacted together at 100-150 deg.C for 2-20hr in an inert gas atmosphere in an inert organic solvent (e.g., diethyl ether) containing metallic Mg and, if desired, the product is hydrolyzed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method C1 for producing organosilicon polymer compounds, particularly polycarbosilane polymers and/or polysilphenylene polymers.

Regarding the production of polycarbosilane polymers, a method using pyrolysis wheel knitting of cyclic or chain-shaped boririran is known (see Japanese Patent Application Laid-open No. 12630/1983), but this method requires 3 steps. ) The yield is low at about 60%, 2) Chain polycarbosilane] (Difficult to obtain coalescence, 3) Dangerous substances such as ZK ligated phosphorus are formed due to thermal decomposition of C2. However, the method of thermally decomposing organomonosilane to obtain an organosilicon polymer having silicon and carbon as main skeletons (Z, anorg, u, allgem, ohem,
286-149-67 (1959)] also has a Tosho acid compound with a molecular weight of about 270. (2) A linear polycarbosilane polymer is obtained (there is a drawback that it is difficult to obtain a linear polycarbosilane polymer).

The present invention relates to a method for producing polycarbosilane polymers and polysilphenylene polymers that solves these disadvantages, and is based on the general formula R"MgX (R" is an unsubstituted or substituted monovalent hydrocarbon). A Grignard reagent represented by a group (-X + 1 halogen atom) selected from a group, a triorganosyl alkyl group, a lylphenyl group, and a general formula X-8
i (R 3
It is characterized in that a mixture of one or more organosilicon compounds represented by X and halogen atoms (n is 1 or 2) is reacted with red sea bream metal in an organic solvent.

To explain this, 1. As a result of extensive research on the production method of organic silicon simple molecular compounds such as polysilane polymer and polysilphenylene compound, the starting material is represented by the above general formula RMgX. When a mixture of the Grignard reagent and one or more general formula silicon compounds is reacted with metallic magnesium, an organosilicon straight molecular compound can be obtained. Also, when this is hydrolyzed, a feminine polycarbosilane can be easily obtained. As a result of further research, we found that this reaction can be carried out in a polar solvent. The present invention was completed by confirming that it is possible to obtain an organosilicon straight molecular compound having a volume of gt2 and a controlled degree of polymerization.

The Grignard reagent used in the method of the present invention has the general formula RlMgX, where R1 is an unsubstituted or substituted monovalent hydrocarbon group, and l2 is a methyl group -
Alkyl groups such as ethyl group, globyl group-butyl group, aryl group such as phenyl group, or groups in which a part of the hydrogen atoms of these groups are substituted with cyano group, halogen atom, etc. Further examples include groups selected from triorganosylalkyl tails such as trimethylsilylmethyl groups, and sylphenyl groups, where X is a halogen group such as chlorine or odorant, and in addition, Examples include ethylmagnesium chloride, phenylmagnesium chloride, trimethylsilylmethylmagnesium chloride, and trimethylsilylphenylmagnesium chloride.

Further, in the organosilicon compound having the above general formula, R is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, or a globyl group.

Alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups, and even these groups σ] A group in which a part of the hydrogen atoms bonded to the carbon atom is substituted with a cyano group-halogen atom, etc., and -R is Divalent hydrocarbon groups such as methylene group, ethylene group, globylene thread, phenylene group,
is a halogen atom such as chlorine, bromine, etc., and n is a number from 1 to 2, /, ) is also Ul, and this (2 is dimethylgloromethylgloa silane, dimethylglorophenylglorosilane -) tylphenyl Examples include gloromethylchlorosilane, dimethylbromomethylguaolyran, methylglochiglobilglochivlan, bisglochithylmethylmethylglochivlan, etc., and these are used as a mixed sand of one or more of them. .

This synthesis reaction generally involves first synthesizing a Grignard reagent in a system consisting of 1m magnesium and an inviscous mixing bath medium.
Next, a nitrogen compound represented by the general formula This is carried out by adding System C2 and then adding the above-mentioned organosilicon compound to System C2. In this reaction, the following formula σ] reaction occurs first, this reacts with mag4s i/ium in the system, the reaction of the following formula occurs, and then) By repeating 1゛2n C2, the polymer compound is It is thought that it will continue to grow. In this case, Grignard reagent σ) If the amount used is large, the degree of polymerization of the obtained polymer will be low, and if it is decreased, the degree of polymerization will be crystallized σ], and the amount of Grignard reagent used is 20 mol% or less of metallic magnesium. It is preferable to do so.

The amount of the organosilicon compound added is preferably 0.9 to 1.1 times the amount of gold layer magnesium (2 to 2).

As mentioned above, this reaction is carried out in an inert organic solvent containing the dimetallic magnelium, and examples of the solvent include ether thread bath agents such as diethyl ether-7-)lahydrofuran, hexamethylphosphoric triamide, etc. σ)
Examples include phosphoric acid amide static agents, benzene, and hydrocarbon solvents such as toluene, but these may be used alone or as a mixed solvent of two or more thereof.

The method of the present invention (the above-mentioned polymerization reaction in two
It is best to carry out the reaction at 0°C, preferably in the lrA range of 40 to 100°C.When adding an organic silicon compound as a starting material to the reaction system, if the addition time is short, a low-molecular cyclized product will be formed. ] - This is preferably carried out for a period of 2 to 20 hours. In addition, if oxygen is present in this reaction system, there is a risk that the Grignard reagent will react with oxygen and stop the polymerization at the reaction step indicated by =ir, so the reaction should be carried out under an atmosphere of inert gas such as nitrogen or argon. That's good.

This is because the organosilicon straight molecular compound obtained in this manner has a terminal of 2 n -□ Si (RMgX).

-n If this is hydrolyzed to form R n -□ 81 (R3H) -n an extremely stable compound can be obtained. According to the method C2 of the present invention, compared to the conventional heat transfer method, the yield is higher and the polymerization degree is controlled. Levosilane polymer, polysilphenylene small polymer IC, σ] Organosilicon straight molecular compounds can be obtained easily and inexpensively.

Next, examples of the method of the present invention will be given.

Example 1 12 g of metallic magnesium (0,
5 mol) and 250ml of tetrahydrofuran.
Under a nitrogen gas atmosphere, 25 ml of tetrahydrofuran containing 1 mole of methylmagnesium chloride prepared in advance was added.

Next, 71.5 g of dimethylchloromethylchlorosilane (
0.5 mol) was added dropwise over 4 hours at an internal temperature of 50 to 60°C.

Next, after this dropwise addition was completed, the reaction mixture was aged for 2 hours at an internal temperature of 66°C, and then cooled and filtered under reduced pressure.
When the solvent was distilled off from the solution under reduced pressure, 3 was obtained with a yield of 86%.
1 g of a viscous solid solid oxide was obtained, and it was confirmed that this was an organosilicon straight molecule compound represented by the following formula with a mean molecular weight of 2,000 to 3.000.

Example 2 12 g safe magnesium (0
, 5-[:/shi) and 250 ml of tetrahydrofuran, and in a nitrogen gas atmosphere, 2.7 g of ethyl bromide (
Ethylmagnesium bromide was produced by dropping 0.025 mol of mol at an internal temperature of 30°C.

Next, add 7 dimethylchloromethylchlorosilane to this system.
1.5 g (0.5 mol) was added dropwise over 4 hours at an internal temperature of 50 to 70°C, and after aging for 2 hours at an internal temperature of 66°C, the reaction mixture was hydrolyzed in a saturated ammonium chloride water bath and dispersed. When the solvent was distilled off under reduced pressure from the apricots obtained, 32g
A liquid molecular substance with a viscosity of 1 Δ] was obtained with a yield of 89%, and its Jt was analyzed. )
It was an organosilicon straightforward molecular compound represented by the following formula: %.

Example 3 Dimethylchloromethylchloroz/ in Example 12
La:”) (-1j)+ 182 methyl phenyl #
102.5. ．． 9 (0.5 mol) was used, but a viscous liquid polymeric composition of 609 was obtained with a yield of 90%, which had a molecular weight of 4.
It was confirmed that it was a simple molecular compound represented by the following formula of 000 to 5,000.

Implementation Ita 114 Dimethylglolomethylcry in Example 2.

Dimethylchloromethylchlorosilane 3 instead of silane
The process was carried out in the same manner as in Example 2, except that 5.7 g (0.25 mol) and dimethylglorophenylgulo-a silane 51.3 M (0-25 mol) σ) were used. The yield was 80%. 41 g of solid polymer product was obtained, which I
It was an organic silicate polymer compound having a molecular weight of 3,000 to 5,000.

Example 5 Example 2C: Replacement of dimethylchloromethylchlorosilane in each month with 21 dimethyl chloromethyl chlorosilane 35
．． 7.1o25 mol) and bisglolomethylmethylchloride aa
The same procedure as in Example 2 was carried out except that a mixture of 22 g (0,125 mol) of i/run was used, and 24 g σJ solid molecular product was obtained with a yield of 89%, which had an average molecular M of :3,000 to 5.000, and was an organosilicon crystal molecule compound represented by the following formula 5.

Claims (1)

[Claims] 1 General formula R'MgX (R" is unsubstituted or substituted'
) A Grignard reagent represented by a group selected from a monovalent hydrocarbon group, a triorganosyl alkyl group, and a sylphenyl group, where X is an halogen atom. General formula % Formula % (3) (R2 is an X atom or a monovalent hydrocarbon group, R3 is a carbonaceous to 6 divalent hydrocarbon group, X is a halogen atom, n is 1 or 2) 1. A method for producing a quasi-organic polymer compound, which comprises reacting a mixture of one or more elementary compounds with metal magi sium in a bath medium. 2. The value used for Grignard reagent is residual magnesium l.
2. The method for producing an organosilicon-based molecular compound according to claim 1, wherein the amount is 20 molar or less.