Thermal reactive hazards of 1,1-bis(tert-butylperoxy)cyclohexane with nitric acid contaminants by DSC

• Published in: Journal of thermal analysis and calorimetry Vol. 109; no. 3; pp. 1253 - 1260
• Main Authors: Hsueh, Kuang-Hua, Chen, Wei-Ting, Chu, Yung-Chuan, Tsai, Lung-Chang, Shu, Chi-Min
• Format: Journal Article Conference Proceeding
• Language: English
• Published: Dordrecht Springer Netherlands 01.09.2012; Springer
• Subjects: Analytical Chemistry; Applied sciences; Chemical engineering; Chemistry; Chemistry and Materials Science; Exact sciences and technology; Inorganic Chemistry; Measurement Science and Instrumentation; Physical Chemistry; Polymer Sciences; Safety; butylperoxy)cyclohexane (BTBPC; Differential scanning calorimetry (DSC); 1,1-Bis; Curve-fitting method; Nitric acid; Thermokinetic parameters; Differential scanning calorimetry; (BTBPC) Curve-fitting method; Binary mixture; Peracetal; 1,1-Bis(tert-butylperoxy)cyclohexane; Concentration effect; Thermal analysis; Reaction runaway; Thermokinetics; Curve fitting; Organic peroxide; Hazard
• ISSN: 1388-6150; 1588-2926; 1572-8943
• DOI: 10.1007/s10973-012-2338-y

With two active O–O peroxide groups, 1,1-bis( tert -butylperoxy)cyclohexane (BTBPC) has a certain degree of thermal instability. It is usually used as an initiator in chemical processes, and therefore reckless operation may result in serious thermal accidents. This study focused on the runaway reactions of BTBPC alone and mixed with various concentrations of nitric acid (1, 2, 4, and 8 N). The essential thermokinetic parameters, such as exothermic onset temperature ( T o ), activation energy ( E a ), frequency factor ( A ), time to maximum rate under adiabatic condition (TMR ad ) and time to conversion limit (TCL), were evaluated by differential scanning calorimetry at the heating rate of 4 °C min −1 , and a kinetics-based curve fitting method was used to assess the thermokinetic parameters. All the results indicated that BTBPC mixed with one more than 4 N nitric acid dramatically increased the degree of thermal hazard in the exothermic peak and became more dangerous. However, it was relatively safe for BTBPC mixed with less than 1 N nitric acid under 34.5 °C.