The thermal stability and the thermal degradation products of high impact polystyrene / decabromodiphenylether / antimony oxide (HIPS FR) have been studied in situ with derivative thermogravimetry (DTG), temperature resolved pyrolysis-mass spectrometry (Py-MS) and pyrolysis-gas chromatography / mass spectrometry (Py-GC /MS). With in-source temperature resolved Py-MS (negative ions) the thermal degradation processes of HIPS FR have been studied dynamically and antimony (oxy)bromides and brominated higher styrene oligomers upto n = 15 have been detected. During degradation of the HIPS FR polymer matrix several processes take place, such as debromination of the flame retardant decabromodiphenylether to form less brominated diphenylethers, bromination of polystyrene and formation of antimony bromides and antimony oxybromides. The formation of toxic polybrominated dibenzofurans (PBDFs) has been shown to occur in the temperature range in which the HIPS FR polymer matrix degrades (350-400°C). This is explained by debromination of decabromodiphenylether to form less brominated diphenylethers which are much more reactive towards formation of PBDFs. © 1991.
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