Chlorosilanes trichlorosilane

On the commercial scale silicone resins are prepared batchwise by hydrolysis of a blend of chlorosilanes. In order that the final product shall be cross-linked, a quantity of trichlorosilanes must be incorporated into the blend. A measure of the functionality of the blend is given by the R/Si ratio (see Section 29.3). Whereas a linear polymer will have an R/Si ratio of just over 2 1, the ratio when using trichlorosilane alone will be 1 1. Since these latter materials are brittle, ratios in the range 1.2 to 1.6 1 are used in commercial practice. Since chlorophenylsilanes are also often used, the CH3/CgH5 ratio is a further convenient parameter of use in classifying the resins. 

FIGURE 4.4 The production of polycrystalline silicon for the eleetronics industry involves several ehemieal steps aimed at the reduetion of impurities. These inelude (1) reaction of metallurgical grade silicon to produce a mixture of chlorosilanes, (2) distillation of trichlorosilane, and (3) reduction of trichlorosilane to polycrystalline silicon. Excerpted by special permission from Chemical Engineering, June 10, 1985. Copyright 1985 by McGraw-Hill, Inc., New York, NY 10020. 

To prepare multifunctionalized symmetric organosilicon compounds by the polyalkylation of benzene. (2-chloroethyi)trichlorosilane and (3-chloropropyl)tri-chlorosilane were reacted with benzene. Polyalkylations of benzene with (2-chloroethyl)silane and (3-chloropropyl)silane were carried out in the presence of aluminum chloride catalyst at a reaction temperature of 80 C. The reaction of benzene with excess (2-chloroethyI )trichlorosilanes afforded pcralkylated product, hexakis(2-(trichlorosilyl)ethyl)benzene in good yield (70%). ... 

Mixing trichlorosilane, acetonitrile and diphenylsulphoxide, carried out at 10°C, detonated. This accident was put down to the exothermic addition reaction of the silicon-hydrogen bond on the carbon-nitrogen triple bond of nitrile. Other interpretations are possible for instance, the effect of traces of hydrogen chloride formed by the hydrolysis of chlorosilane on acetonitrile. 

When great care is taken to use pure reagents, 10-7 mole of chloroplatinic acid per mole of product causes this addition to occur rapidly near room temperature and to go to completion to give analytically pure ethyltri-chlorosilane (100% yield based on trichlorosilane). 

It is seen that the trichlorosilane reacts with the silanol groups to form siloxane bridges. Subsequently the residual chlorines are hydrolyzed. Under carefiiUy controlled reaction conditions it is possible to obtain a product in which the hydrocarbonaceous layer at the surface is similar to that in a corresponding monomeric bonded phase. However, the hydrolysis of chlorines that did not react with surface silanbis may result in a silanol concentration at the surface that is higher than that in the silica gel proper used as the starting material for the reaction with alkyltri-chlorosilanes. 

Conductometric measurements were used in a recent study of the hydrolysis of alkyldi- and trichlorosilanes in polar solvents by Shaffer and Flanigen (66). A first order dependence on water concentration and a second order dependence on chlorosilane was observed for the hydrolysis of trichlorosilanes. The dichlorosilanes evinced a highly anamolous negative order. For the trichlorosilanes the data are consistent with a mechanism that assumes the following steps ... 

The first rectification stage. From collector 10 the mixture of methyl-chlorosilanes is periodically fed into pressure container 11, from where at 50-65 °C it is sent through heater 12 (by self-flow) onto the feeding plate of rectification tower 13. From the tower the tank liquid (methyltrichloro-silane, dimethyldichlorosilane and tank residue) flows into tank 14, where the temperature of 80-90 °C is maintained, and from there is continously poured into collector 22. After the tower, vapours of the head fraction at a temperature below 58 °C, consisting of the rest of methylchloride, di- and trichlorosilane, dimethylchlorosilane, methyldichlorosilane and the azeotropic mixture of silicon tetrachloride and trimethylchlorosilane are sent into refluxer 15, cooled with water, and into refluxer 16, cooled with salt solution (-15 °C). After that, through cooler 17 the condensate is gathered in receptacle 19. Volatile products, which did not condense in reflux-ers 15 and 16, are sent into condenser 18 cooled with Freon (-50 °C). There they condense and also flow into receptacle 19. As soon as it is accumulated, the condensate is sent from receptacle 19 into collector 20. 

Among the silicon halides, the chlorosilanes have attracted by far the greatest attention. Silicon tetrachloride, trichlorosilane and the methylchlorosilanes are produced on an industrial scale and are used, for instance, in the production of pure silicon or silicones. 

These considerations seem to rule out the Shtetter synthesis, for this method produces trichlorosilanes with chlorine atoms in the organic groups. Processes for converting these into ethyl- or methyl-chlorosilanes have not been published supposedly such conversions would have to be extremely simple if the combined procedures are to retain an advantage over the Grignard and direct methods. As such methods of conversion are lacking, the Shtetter synthesis probably will reach commercial importance only after further research has demonstrated how use may be made of its interesting products. 

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