Autocatalytic decomposition properties and thermal decomposition of benzoyl peroxide

Differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA) were used to examine the thermal decomposition of benzoyl peroxide (BPO). The interruption rescanning method was adopted to examine the effect of thermal history on the autocatalysis and thermal decomposition of BPO. Autocatalysis of BPO was verified through isothermal experiments. According to the DSC linear temperature rise data of BPO, mathematical methods were used to decouple and divide the peaks. Kinetic analysis using both the Kissinger and Friedman methods was performed. The initial decomposition temperature of the decoupled BPO ranged between 101.4 and 104.6 °C. The peak temperature was 110.9–126.2 °C, and the decomposition enthalpy was 229.7–524.2 J g–1. The apparent activation energy was higher in the coupling state than after decoupling one. The thermal history and isothermal experiments demonstrated that BPO possessed autocatalytic properties. Results revealed that initial decomposition temperature tended to decrease with the increase in interruption temperature. In addition, the apparent activation energy of BPO decreased following the thermal history analysis because of the formation of intermediate products from BPO in the thermal history experiments, which further promoted BPO’s thermal decomposition. This effect led to a decrease in BPO’s initial decomposition temperature.