Pyrolysis of hexamethyldisiIoxane (HMDS) and its copyrolysis with chlorotrimethylsilane and tetrachtorosilane were studied. Based on the data of GLC analysis and on the mass spectrum of the condensate obtained after the pyrolysis of HMDS, it was concluded that HMDS acts as a source of dimethytsilanone. The results of the copyrolysis of HMDS with chlorotrimethylsflane used as a trapping reagent indicate that the dimethylsilanone generated from HMDS can be inserted into the Si--CI and Si--O bonds. In the copyrolysis of HMDS with tetrachlorosilane serving as a trapping reagent for dimethylsilanone, both dimethylsilanone and dichlorosilanone are generated.
The pyrolysis of trichlorosilane in the presence of different amounts of chloroform and the copyrolysis of HSiCI 3 with buta-l,3-diene in the presence of I tool.% chloroform were studied. The enthatpies of formation of products resulting from the pyrolysis of HSiCI 3 in the presence of chloroform were calculated by the quantum chemical method. Based on the thermochemical data as well as data from GLC and mass spectrometry, it was concluded from the condensate composition that introduction of chloroform into the zone of pyrolysis of HSiCI 3 favors generation of silylenes.
PyroIysis of trichlorosilane (TCS) and copyrolysis of TCS with 1,3-butadiene were studied_ The enthalpies and activation energies for the reactions of the products of TCS pyrolysis were found by quantum-chemicaL calculations. A direct study of the pyrolysis of TCS by mass spectrometry was carried out. Based on the thermochemical parameters found by quantum-chemical calculations and on the results of GLC and mass spectrometry concerning the composition of the p~TOI.VSiS products, it was concluded that the pyrolysis of TCS follows a scheme that includes formation of radicals and silylenes.
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