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2749681 
Journal Article 
The Thermal Stability of tert-Butyl Hydroperoxide-Acid Mixtures 
Andreozzi, R; Caprio, V; Crescitelli, S; Russo, G 
1988 
Yes 
Journal of Hazardous Materials
ISSN: 0304-3894
EISSN: 1873-3336 
NIOSH/00180755 
17 
3 
305-313 
Safety problems related to potential explosions during the production of di-tert-butyl-peroxide (DTBP) were studied by investigating the behavior of tert-butyl-hydroperoxide (TBHP) mixtures with acid. All the mixtures studied were prepared using TBHP 70 percent in water solution and p-toluenesulfonic-acid (PTSA) (solid 95 percent). Temperatures recorded with an accelerating rate calorimeter at different molar ratios of TBHP to PTSA showed an accelerating rise in temperature beginning at a time determined by the molar ratio. Results with a reaction calorimeter and gas chromatography indicated that the main product was DTBP, with a maximum yield of 32.5 percent, corresponding to 56.0 percent of reacted TBHP and to an adiabatic temperature rise of 35 degrees-C. The data indicated exothermic reactions with possible runaway potential, with the temperature of first reactivity appearing at as low as 50 degrees-C. Addition of 2 percent acetone to the reaction mixture considerably enhanced the reactivity, an important finding since acetone could be produced as a byproduct of the DTBP synthesis. Acetone produced in this way could react with TBHP and other peroxides, inducing their thermal decomposition. Formation of acetone and other reaction products was temperature dependent. The authors conclude that for a complete understanding of safety problems relating to DTBP production, a detailed knowledge of the mechanism operating in the system under normal and anomalous conditions is necessary.