Evaluation of a tert-Butyl Peroxybenzoate Runaway Reaction by Five

RESEARCH NOTE pubs.acs.org/IECR

Evaluation of a tert-Butyl Peroxybenzoate Runaway Reaction by Five Kinetic Models Jo-Ming Tseng Institute of Safety and Disaster Prevention Technology, Central Taiwan University of Science and Technology, 666, Buzih Rd., Beitun District, Taichung, Taiwan 40601, Republic of China

Yan-Fu Lin* Department of Chemistry, National Chung Hsing University, 250 Kuo-Kwang Rd., Taichung, Taiwan 40227, Republic of China ABSTRACT: This study focuses on understanding the basic kinetic parameters associated with runaway reactions for tert-butyl peroxybenzoate (TBPB), which is a strong free-radical source. TBPB is used as a polymerization initiator, catalyst, vulcanizing agent, cross-linking agent, and chemical intermediate. Runaway reactions can either be induced by hot spots or caused by insufficient heat removal. It is important to understand the decomposition reactions that may result in a runaway reaction. To do so, one must evaluate the thermal kinetic parameters, such as activation energy, frequency factor, and reaction order to make the process safer. Most investigations focus on methyl ethyl ketone peroxide, di-tert-butyl peroxide, and cumene hydroperoxide. The kinetic parameters indicate the degree of thermal hazard based on accidents triggered by TBPB. This study uses mathematical models of the Coats
Redfern equation, the Arrhenius equation, the corrected kinetic equation, the Kissinger equation, and the Ozawa equation to study these kinetic parameters.

’ INTRODUCTION tert-Butyl peroxybenzoate (TBPB) is a strong free-radical source containing more than 8.1% active oxygen. TBPB is used as a polymerization initiator, catalyst, vulcanizing agent, crosslinking agent, and chemical intermediate.1 The decomposition of TBPF is rapid, causing fire and explosion hazards when heated and under the influence of light. It reacts violently with incompatible substances or ignition sources, including acids, bases, reducing agents, and heavy metals. Thus, it should be stored in a dry and refrigerated (0.93 in three kinetic models. The kinetic models used in this study included the corrected kinetic equation, the Kissinger equation, and the Ozawa equation. Our results show that TBPB advances the exothermal reaction under lower Ea values. The free-radical chain reaction was easily triggered under decomposition, because of the thermal decomposition mechanisms of TBPB. The

Figure 6. Activation energy analysis for TBPB with scanning rates of 1, 2, 4, and 10 °C/min, using the Ozawa equation.

reaction order for TBPB was ∼0
1 when using the Arrhenius equation and the Coats
Redfern method. Furthermore, because the TBPB concentration in our experiment was high, the reaction order could range from the pseudo-zero order to first order, depending on which method was used. When the reaction order for TBPB ranges from 0 to 1, the results support the hypothesis that the O
O bond homolytic cleavage step is the rate-determining step. Therefore, TBPB should be well-controlled when used in the manufacturing process, not to mention its explosive power.

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected].

’ ACKNOWLEDGMENT We are grateful to Prof. Chi-Min Shu from the Graduate School of Engineering Science and Technology, National Yunlin 4786

dx.doi.org/10.1021/ie100640t |Ind. Eng. Chem. Res. 2011, 50, 4783–4787

Industrial & Engineering Chemistry Research University of Science and Technology, Yunlin, Taiwan, ROC, for his technical assistance in this study.

’ NOMENCLATURE A = pre-exponential factor (m3/(mol s)) Ea = activation energy (kJ/mol) K = heat conduction coefficient (W/(m K)) R = gas constant (8.31415 J/(K mol)) T0 = exothermic onset temperature (°C) T0i = exothermic onset temperatures of different scanning rates (where i = 1, 2, 3, 4) (°C) Tf = final temperature (°C) Ti = peak temperature of various scanning rates (where i = P1, P2, P3) (°C) TP = peak temperature (°C) TPi = peak temperature at different scanning rates (where i = 1, 2, 3, 4) (°C) TRi = temperature in various scanning rates at isoconversional degree (where i = 1, 2, 3, 4) (°C) β = scanning rate (°C/min) βi = scanning rate (where i = 1, 2, 3, 4) (°C/min)

RESEARCH NOTE

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dx.doi.org/10.1021/ie100640t |Ind. Eng. Chem. Res. 2011, 50, 4783–4787