Thermal decomposition and thermal hazards analysis of typical organic peroxides with impurities

Organic peroxides in the chemical industry can cause safety risks due to instability, prompting an interest in their thermal stability to avoid dangers. This study investigated the thermal hazards and decomposition mechanisms of cumene hydroperoxide (CHP), dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP), 1,3-bis(tert-butylperoxyisopropyl)benzene (BIBP), and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane (DBPH), and the influence of impurities on these compounds. The thermodynamic properties of these compounds were determined via differential scanning calorimetry (DSC), and their apparent activation energies were calculated by kinetic models. The adiabatic thermal decomposition characteristics were obtained via accelerating rate calorimetry (ARC), and the risk matrix assessment was employed. The decomposition products were characterized via gas chromatography-mass spectrometry (GC–MS), and the corresponding thermal decomposition pathways were proposed. The energy of each step in the proposed pathways was calculated using density functional theory (DFT). The results provide critical guidance for the safe application of these five organic peroxides within the chemical industry.