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Elucidating the Thermal Decomposition of Dimethyl Methylphosphonate by Vacuum Ultraviolet (VUV) Photoionization: Pathways to the PO Radical, a Key Species in Flame‐Retardant Mechanisms
Author(s) -
Liang Shuyu,
Hemberger Patrick,
Neisius N. Matthias,
Bodi Andras,
Grützmacher Hansjörg,
LevaloisGrützmacher Joelle,
Gaan Sabyasachi
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404271
Subject(s) - dimethyl methylphosphonate , chemistry , thermal decomposition , photochemistry , photoionization , decomposition , fire retardant , ultraviolet , inorganic chemistry , organic chemistry , materials science , ionization , ion , optoelectronics
The production of phosphoryl species (PO, PO 2 , HOPO) is believed to be of great importance for efficient flame‐retardant action in the gas phase. We present a detailed investigation of the thermal decomposition of dimethyl methylphosphonate (DMMP) probed by vacuum ultraviolet (VUV) synchrotron radiation and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. This technique provides a snapshot of the thermolysis process and direct evidence of how the reactive phosphoryl species are generated during heat exposure. One of the key findings of this work is that only PO is formed in high concentration upon DMMP decomposition, whereas PO 2 is absent. It can be concluded that the formation of PO 2 needs an oxidative environment, which is typically the case in a real flame. Based on the identification of products such as methanol, formaldehyde, and PO, as well as the intermediates OPCH 3 , H 2 CPOH, and H 2 CP(O)H, supported by quantum chemical calculations, we were able to describe the predominant pathways that lead to active phosphoryl species during the thermal decomposition of DMMP.