For SBR a third devolatilisation reaction, which represented the devolatilisation of additives, was identified. DTA results confirmed the existence of these two devolatilisation reactions. Moreover, the combined DTG and DTA results indicated that the BR and SBR samples started to boil around 450 ◦ C. Next, a combination of model-free and model-based kinetic methods was successfully employed for the modelling of the devolatilisation.