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A mechanistic study of the low pressure pyrolysis of linear siloxanes

Almond, M. J., Becerra, R., Bowes, S. J., Cannady, J. P., Ogden, J. S., Young, N. A. and Walsh, R. (2009) A mechanistic study of the low pressure pyrolysis of linear siloxanes. Physical Chemistry Chemical Physics, 11 (40). pp. 9259-9267. ISSN 1463-9076

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To link to this article DOI: 10.1039/b910549b

Abstract/Summary

Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of 1,1,3,3-tetramethyldisiloxane (L1), 1,1,3,3,5,5-hexamethyltrisiloxane (L2) and 3H,5H-octamethyltetrasiloxane (L3) at ca. 1000 K in a flow reactor at low pressures. The hydrocarbons CH3, CH4, C2H2, C2H4, and C2H6 were observed as prominent pyrolysis products in all three systems, and amongst the weaker features are bands arising from the methylsilanes Me2SiH2 (for L1 and L2) and Me3SiH (for L3). The fundamental of SiO was also observed very weakly. By use of quantum chemical calculations combined with earlier kinetic models, mechanisms have been proposed involving the intermediacy of silanones Me2Si = O and MeSiH = O. Model calculations on the decomposition pathways of H3SiOSiH3 and H3SiOSiH2OSiH3 show that silanone elimination is favoured over silylene extrusion.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:10961
Uncontrolled Keywords:THERMAL-DECOMPOSITION, TRIMETHYLSILANE, DIMETHYLSILANE, SILYLENE, KINETICS, SILANES
Publisher:Royal Society of Chemistry

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