Chemistry and Technology of Silicones by Walter Noll

By Walter Noll

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Th e e-phas e o f th e Cu/S i system , correspondin g approximatel y to C u S i , als o yield s dimethyldichlorosilan e selectivel y (274). 3 15 4 This realizatio n o f th e importanc e o f a n intermetalli c phas e a s th e cata lytically activ e componen t an d th e assumptio n o f a partiall y pola r natur e fo r the C u — S i bon d le d t o th e ide a tha t th e primar y ste p i n th e reactio n wit h methyl chlorid e wa s th e dissociativ e adsorptio n o f thi s molecule . Th e subse quent step s unti l a dimethyldichlorosilan e molecul e i s detache d fro m th e surface ar e show n i n th e schem e belo w (274) (wher e M indicate s th e bod y o f the metal) .

4 . 1 ) . 2 . 3 . , R L i + C l — S i — -> R — S i — + LiCl Reactions of this kind are formally analogous to the reaction of a Grignard compound with a functional silicon compound. The organic group can, however, also be transferred by treating an organic halide with a halosilane in the presence of an alkali metal. In other words, the reaction is carried out in the manner of a Wurtz synthesis. 3). However, this group of reactions has not become even remotely as important for actual silicone chemistry as the Grignard synthesis or even the direct synthesis.

Initially, it was merely to attempt to influence the heat balance of the reaction by adding nitrogen to the organic halide. Additions of 2 5 to 5 0 % nitrogen have been recommended (252). This, however, makes the condensa­ tion of the reaction products more difficult, especially when their boiling points are low. Numerous attempts have been made to influence the yield and composition of the reaction products with suitable additives. Mixing hydrogen with methyl chloride results in only a slight increase of the yield of C H S i H C l ( 2 5 7 ) .

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