Methylchlorosilanes determination

Direct Process. Passing methyl chloride through a fluidized bed of copper and siUcon yields a mixture of chlorosilanes. The rate of methylchlorosilane (MCS) production and chemical selectivity, as determined by the ratio of dimethydichlorosilane to the other compounds formed, are significantly affected by trace elements in the catalyst bed very pure copper and siUcon gives poor yield and selectivity (22). 

The evolution of methylchlorosilanes between 450 and 600 K is consistent with the 550 - 600 K typical for the catalytic Rochow Process [3]. It is also reasonably consistent with the evolution of methylchlorosilanes at 500 - 750 K reported by Frank and Falconer for a temperature programmed reaction study of the monolayer remaining on a CuaSi surface after catalytic formation of methylchlorosilanes from CHaCl at higher pressures [5]. Both of these observations suggest that the monolayer formed by methyl and chlorine adsorption on pure CuaSi is similar to that present on active catalysts. For reference, methylchlorosilanes bond quite weakly to tiie surface and desorb at 180 - 220 K. It can thus be concluded that the rate-determining step in the evolution of methylchlorosilanes at 450 - 600 K is a surface reaction rather an product desorption. 

The formation of tri- and especially tetrasilanes which are already branched (tertiary Si-units) as the first reaction products (described elsewhere [4]) suggests the appearance of intermediate silylene species which could enter in insertion reactions of Si-Si as well as Si-Cl bonds. The tri- and tetrasilanes undergo thermal crosslinking reactions at reaction temperatures of 165-250 °C. In addition dehydrochlorination reactions initiated by acid H-abstraction of methyl groups cause the formation of carbosilane (methylene) units in the polymer framework. Table 1 shows the gross compositions of poly(methylchlorosilanes) which are determined by the reaction temperature. 

This approach was applied to the determination of silica surface distribution functions on reaction constants of organosilicon compounds chemisorption using the Gamma distribution on k (Table 4). The distribution functions on Ink were calculated on the basis of chemisorption kinetic isotherms for methylchlorosilanes (CH3)4 nSiCln (n from 1 to 4) and for the compounds (CH3)3SiX X = Cl, CN, N3, NCO, NCS, 0Si(CH3)3 on the non-porous dehydrated silica surface [4,22]. As shown in [57] the correlation is observed between the logarithms of rate constants with the sum of inductive constants of substituents at Si atom in (CH3)4 nSiCln compounds ([Pg.269]

Burson and Kenner determined the purity of trichlorosilane and silicon tetrachloride with the SF-96 column. DC-LSX-3-0295 tri-fluoropropyl silicone gum was found to be the best for analysing samples of the methylchlorosilanes. Figure 57 shows a chromatogram of a sample of methyltrichlorosilane containing as impurities 0.02% silicon tetrachloride, 0.03% methyldichlorosilane, 0.04% trimethyl-chlorosilane, 0.12% dimethyldichlorosilane, and 0.07% 1,1,3,3,-tetra-chloro-1,3-dimethyldisiloxane. The concentrations of these impurities were determined by comparison of peak areas with standards prepared by adding known amounts of these impurities to methyltrichlorosilane of 99.99% purity. 

---