Prediction of thermal hazard for TBPTMH mixed with BPO through DSC and isoconversional kinetics analysis

Abstract

tert-Butyl peroxy-3,5,5-trimethylhexanoate (TBPTMH), generally used as an initiator, can replace tert-butyl peroxybenzoate (TBPB) in polymerization processes. The thermal behavior of TBPTMH added to this reaction was analyzed. Furthermore, we compared the influence on thermal hazards with TBPB and benzoyl peroxide. Through differential scanning calorimetry and isoconversional kinetics analysis, thermokinetic parameters and simulation results, including apparent activation energy (Ea), time to maximum rate under adiabatic conditions (TMRad), and self-accelerating decomposition temperature (SADT), can be used to identify a safer handling environment when TBPTMH is mixed with tert-butyl peroxide. According to DSC thermal curves, the apparent exothermic onset temperature of TBPTMH was from 100 to 124 °C, and the heat of decomposition of TBPTMH was from 748.81 to 950.48 J g−1. Ea values as calculated using three methods (Ozawa–Flynn–Wall, Friedman, and ASTM E698) were 122.4, 122.7, and 122.0 kJ mol−1, respectively. From the point of view of thermal loss prevention, TMRad and SADT are two crucial safety parameters, which were obtained as 61.3 °C under 24 h and 55.0 °C, respectively.