Thermal hazard assessment of tert-butyl perbenzoate using advanced calorimetric techniques and thermokinetic methods

Abstract

Tert-butyl perbenzoate (TBPB) is a common organic peroxide initiator in the polymer sector, and its thermal behavior and potential dangers are explored in this quantitative study. Advanced calorimetric techniques and thermokinetic models were used to examine the thermal stability and breakdown features of TBPB. During the first stage of the TBPB synthesis, the process safety analysis revealed a very exothermic reaction. Peak temperatures for TBPB thermal decomposition ranged from 133.37 to 156.64 °C, with heat release values of roughly 1279 ± 135 J/g, as determined by differential scanning calorimetry and thermogravimetric analysis. Apparent activation energies ranged from 78.78 to 133.92 kJ/mol in a thermokinetic analysis employing the Kissinger, Starink, ASTM E698, Friedman, Kissinger-Akahira-Sunose, and Flynn-Wall-Ozawa models. Based on multiple nonlinear regression analysis, a two-step reaction mechanism was postulated, one involving an autocatalytic reaction and the other involving a reaction of the nth order. In order to evaluate the thermal dangers related with TBPB, the self-accelerating decomposition temperature (SADT) and thermal risk index (TRI) were calculated. Based on TRI calculations, TBPB was assessed as having low thermal risk, with SADT values ranging from 40 to 60 °C depending on package size. These numerical findings add to our knowledge of the thermal risks posed by TBPB and shed light on how best to handle, store, and transport the compound for use in industrial settings.