Investigation on the formation mechanism of main products from TBBPA pyrolysis using DFT method.

The formation mechanisms of the main pyrolysis products of tetrabromobisphenol A (TBBPA) such as hydrogen bromide (HBr), bisphenol A compounds, and phenolic compounds were studied through using density functional theory (DFT) method at the theoretical level of B3P86/6-311 + G (d,p), and the effects of H and Br radicals on the formation mechanism of each product were analyzed. For the formation of each pyrolysis product, this paper presented various possible reaction pathways and acquired their thermodynamic parameters. Calculation results show that HBr can be produce. d continuously during the pyrolysis of TBBPA, and combination and abstraction reactions are the main ways for the generation of HBr. Br radical can abstract H atom from the phenolic hydroxyl groups of TBBPA to produce HBr, and this reaction is barrierless. When H radicals are involved in the initial reaction, the significance of the keto-enol tautomerism is negligible at all debrominations. The Br atom abstraction by H radical is the optimal pattern for debromination. TBBPA can be transformed into low-brominated bisphenol A through consecutive hydrodebromination reactions with trivial activation energies of 8.7-9.5 kJ/mol. The demethylation reaction is an initiation reaction for monomolecular pyrolysis of TBBPA and low-brominated bisphenol A, which is beneficial to the formation of phenolic compounds. During the pyrolysis of TBBPA, para-position Br atom of polybrominated phenol is easier to be removed and the energy barriers of rate-determining steps of the optimal reaction paths for the formation of 2,4,6-tribromophenol, 2,6-dibromophenol, 2,4-dibromophenol, 2-bromophenol, 4-bromophenol and phenol are 108.8, 7.6, 8.7, 8.1, 9.5, and 8.7 kJ/mol, respectively.