The direct synthesis of methylchlorosilanes I. Steady-state and transient reaction kinetics
作者： Jong Pal Kim , David G Rethwisch
DOI: 10.1016/0021-9517(92)90219-8
关键词: Selectivity 、 Steady state (chemistry) 、 Tin 、 Dimethyldichlorosilane 、 Chemistry 、 Chemical kinetics 、 Order of reaction 、 Inorganic chemistry 、 Reaction rate 、 Zinc
摘要: Abstract Reaction kinetics under steady-state and transient conditions were used to study the effects of catalyst (copper) promoters (zinc tin) on direct reaction methyl chloride with silicon produce methylchlorosilanes. Use infrared spectroscopy allowed rapid analysis gas-phase product composition. This accurate measurement apparent activation energy order for each product. An improved method calculating rates is also introduced. Addition Zn as a promoter Cu did not change overall rate but increased selectivity more methylated silanes. Tin promotion chlorinated silanes, while having little affect rate. Copromotion zinc tin rate; however, dimethyldichlorosilane (DMDC) was dependent concentration tin. A trace amount (ca. 0.005-0.01 wt%) produced highest DMDC; increasing 0.2 wt% decreased selectivity. We propose that primary role dissociative adsorption McCl such group attached Si Cl Zn.
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sci-hub.se 参考文章(11)
R. C. Poller, The chemistry of organotin compounds ,(1970)
R. J. H. Voorhoeve, Organohalosilanes. Precursors to Silicones ,(1967)
W WARD, Catalysis of the Rochow Direct Process Journal of Catalysis. ,vol. 100, pp. 240- 249 ,(1986) , 10.1016/0021-9517(86)90089-8
Timothy C Frank, Keith B Kester, John L Falconer, Catalytic formation of silanes on copper-silicon alloys Journal of Catalysis. ,vol. 91, pp. 44- 53 ,(1985) , 10.1016/0021-9517(85)90286-6
LD Gasper-Galvin, DM Sevenich, HB Friedrich, DG Rethwisch, Role of metallic promoters in the direct synthesis of methylchlorosilanes Journal of Catalysis. ,vol. 128, pp. 468- 478 ,(1991) , 10.1016/0021-9517(91)90304-M
W BANHOLZER, Characterization of reactive areas in the direct process for the production of methylchlorosilanes Journal of Catalysis. ,vol. 114, pp. 259- 270 ,(1988) , 10.1016/0021-9517(88)90029-2
Dietmar Seyferth, Comprehensive Organometallic Chemistry Organometallics. ,vol. 3, pp. 1135- 1135 ,(1984) , 10.1021/OM00085A900
A I Gorbunov, A P Belyi, G G Filippov, Reactions of Silicon and Germanium with Halogens, Their Hydrides, and Organic Halogen Derivatives Russian Chemical Reviews. ,vol. 43, pp. 291- 304 ,(1974) , 10.1070/RC1974V043N04ABEH001807
W BANHOLZER, Active site formation in the direct process for methylchlorosilanes Journal of Catalysis. ,vol. 101, pp. 405- 415 ,(1986) , 10.1016/0021-9517(86)90268-X
H.Bruce Friedrich, David M. Sevenich, Lee D. Gasper-Galvin, David G. Rethwisch, Infrared spectroscopic determination of methyl-chlorosilanes from the direct process reaction Analytica Chimica Acta. ,vol. 222, pp. 221- 234 ,(1989) , 10.1016/S0003-2670(00)81897-8