A mechanistic study of the low pressure pyrolysis of linear siloxanes

Almond, Matthew J.; Becerra, Rosa; Bowes, Sarah J.; Cannady, John P.; Ogden, J. Steven; Young, Nigel A.; Walsh, Robin

Abstract

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.

Citation

Almond, M. J., Becerra, R., Bowes, S. J., Cannady, J. P., Ogden, J. S., Young, N. A., & Walsh, R. (2009). A mechanistic study of the low pressure pyrolysis of linear siloxanes. Physical chemistry chemical physics : PCCP, 11(40), 9259-9267. https://doi.org/10.1039/b910549b

• Journal Article Type: Article
• Acceptance Date: Jul 14, 2009
• Publication Date: Oct 21, 2009
• Journal: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
• Print ISSN: 1463-9076
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 11
• Issue: 40
• Pages: 9259-9267
• DOI: https://doi.org/10.1039/b910549b
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://hull-repository.worktribe.com/output/396179