Thermal formation of PBDD/F from tetrabromobisphenol A--a comparison of polymer linked TBBP A with its additive incorporation in thermoplastics.

For a long period, polybrominated flame retardants are under discussion because of the formation of polybrominated dibenzo-p-dioxins (PBDD)/dibenzofurans (PBDF) (PBDD/F) in case of thermal stress. Concerning polymer linked tetrabromobisphenol A (TBBP A), formation of PBDD/F was commonly presumed to be sterically hindered because of the covalent fixation into the polymer backbone. Combustion experiments with additively incorporated TBBP A compared with its polymer linkage revealed, that this assumption is incorrect and has to be revised. Under same conditions, similar PBDD/F concentrations in the range of 17.5-19.6 mg PBBD/F per kg TBBP A applied were analyzed. PBDD/F homologue distribution patterns were almost identical predominated by low brominated PBDF. These findings for PBDD/F formation have to be considered in future discussions regarding thermal stress caused by combustion or recycling processes, including other flame retardants bound in polymer matrix, e.g. polybrominated polystyrene (PS), or those with molecular structures showing less analogy to PBDD/F, like hexabromocyclododecane. The second aspect introduced, is the influence of different plastics on the formation rates of PBDD/F. In this context, combustion experiments were performed in an atmosphere consisting of synthetic air and HBr. PBDD/F concentrations were 8.47 mg/kg polyethylene, 1.67 mg/kg PS, 3.92 mg/kg phenolic resin and 18.1 mg/kg epoxy resin. Distribution patterns of PBDD/F homologues could partly be correlated with the occurrence of the precursors polybrominated benzenes and phenols.