Kinetic and thermal safety analysis for tert-butyl peroxy-3,5,5-trimethylhexanoate by advanced calorimetric technology

• DOI: 10.1007/s10973-016-5778-y
• Publication Date: 2016-08-17T11:17:47Z
• Authors: Yi Yang; Yun-Ting Tsai; Chen-Rui Cao; Chi-Min Shu
• Keywords: Thermal Runaway; Exothermic reaction; Energetic material

Thermal stability parameters were evaluated for the decomposition reaction of tert-butyl peroxy-3,5,5-trimethylhexanoate (TBPMH), a free-radical initiator, by differential scanning calorimetry. According to the results, the apparent exothermic onset temperature, heat of decomposition, and time to maximum rate under adiabatic conditions of TBPMH were 103.0 °C, −924.0 kJ mol−1, and 9.81 min (at 90.0 °C), respectively. A kinetic model was also established under different nonisothermal conditions to evaluate the kinetic behavior of TBPMH by model-free technique and model-fitting method. The self-accelerating decomposition temperature (SADT) was calculated and was similar to that reported in the literature; the SADT values corresponding to various package sizes were also calculated, and an increase in mass caused a drop in SADT. These results can provide a solution to prevent runaway reactions during the storage and transportation of TBPMH, and the applied technique can be a substitute for the complicated procedures and large-scale experiments inherent in traditional analysis methods, thereby preventing process thermal accidents, environmental pollution, and energy depletion.