DFT studies on pyrolysis mechanisms of tetrabromobisphenol A (TBBPA)

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant. In order to better understand the decomposition process of TBBPA and clarify the evolution process of the main pyrolysis products, the density functional theory (DFT) method PBE0/6-311G(d) has been used to investigate the pyrolysis mechanisms of TBBPA in this study. Seven possible pyrolysis reaction paths were proposed, and the kinetic parameters in all pyrolysis paths were calculated. The calculation results indicate that in initial degradation of TBBPA without the involvement of hydrogen radical, the demethylation reaction is the main pyrolysis reaction channel, and the keto-enol tautomerization reaction is the main competitive pyrolysis reaction channel. The brominated cyclohexadienone formed through the keto-enol tautomerization is prone to further debromination to generate Br radical. The involvement of hydrogen radical significantly lowers the energy barrier of TBBPA decomposition. When a hydrogen radical is involved in the pyrolysis process, the debromination reaction becomes the major pyrolysis reaction channel, and the homolytic cleavage of C aromatic –C bond becomes the major competitive pyrolysis reaction channel.