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Thermal parameters study of 1,1-bis(tert-butylperoxy)cyclohexane at low heating rates with differential scanning calorimetry

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Abstract

Having two active peroxide groups, 1,1-bis(tert-butylperoxy)cyclohexane (BTBPC) has a certain degree of thermal instability. It is usually used as an initiator in a chemical process, and therefore, careless operation could result in severe accidents. This study emphasized the runaway reactions of BTBPC 70 mass% (4.5–5.2 mg), the relevant thermokinetic parameters, and the thermal safety parameters. Differential scanning calorimetry was used to evaluate the above-mentioned thermokinetic parameters, using four low heating rates (0.5, 1, 2, and 4 °C min−1) combined with kinetic simulation method. The results indicated that apparent exothermic onset temperature (T o), apparent activation energy (E a), and heat of decomposition (ΔH d) were ca. 118 °C, 156 kJ mol−1, and 1,080 kJ kg−1, respectively. In view of process loss prevention, at the low heating rates of 0.5, 1, 2, and 4 °C min−1, storing BTBPC 70 mass% below 27.27 °C is a more reassuring approach.

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Abbreviations

A :

Pre-exponential factor in the Arrhenius equation (s−1 M1−n)

C p :

Specific heat capacity (J g−1 K−1)

CV:

Coefficient of variation (dimensionless)

E a :

Apparent activation energy of reaction (kJ mol−1)

ΔH d :

Heat of decomposition (kJ kg−1)

k :

Reaction rate constant (mol L−1 s−1)

k o :

Pre-exponential factor of reaction (s−1 M1−n)

m :

Mass of reactant (g)

n :

Order of reaction (dimensionless)

n i :

Reaction order of ith stage (dimensionless)

r i :

Reaction rate of ith stage (g s−1)

SD:

Standard deviation (dimensionless)

ΔT ad :

Adiabatic temperature rise (°C)

TCL:

Time to conversion limit (day)

TER:

Total energy release (kJ kg−1)

T ext :

Extrapolated peak temperature of thermal curve by software of DSC device (°C)

TMR ad :

Time to maximum heating rate under adiabatic conditions (min, h, day)

T m :

Temperature of DSC thermal curve exhibits maximum enthalpy (°C)

T o :

Apparent exothermic onset temperature of decomposition reaction (°C)

T p :

True peak temperature of thermal curve by DSC detector (°C)

\( \overline{X} \) :

Sample mean (variable)

Z :

Autocatalytic constant (variable)

α :

Degree of conversion (dimensionless)

Β :

Heating rate of DSC experiment (°C min−1)

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Acknowledgements

The authors wish to express their gratitude to Dr. Arcady A. Kossoy of ChemInform Saint Petersburg (CISP), Ltd., St. Petersburg, Russia, and Mr. Anthony M. Janeshek of Dow Chemical Co., Freeport, Texas, USA, for providing technical assistance. Furthermore, the authors are indebted to Mr. Chia-Yuan Wen for his help on lab tests.

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Authors and Affiliations

  1. Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology (YunTech), 123, University Rd., Sec. 3, Douliou, Yunlin, 64002, Taiwan, ROC

    Kuang-Hua Hsueh & Wei-Chun Chen

  2. Department of Safety, Health, and Environmental Engineering, Chung Hwa University of Medical Technology, 89, Wen-Hwa 1st Street, Jen-te, Tainan, 71703, Taiwan, ROC

    Kuang-Hua Hsueh

  3. Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology (YunTech), 123, University Rd., Sec. 3, Douliou, Yunlin, 64002, Taiwan, ROC

    Shang-Hao Liu & Chi-Min Shu

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  1. Kuang-Hua Hsueh
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  2. Wei-Chun Chen
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Correspondence to Chi-Min Shu.

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Hsueh, KH., Chen, WC., Liu, SH. et al. Thermal parameters study of 1,1-bis(tert-butylperoxy)cyclohexane at low heating rates with differential scanning calorimetry. J Therm Anal Calorim 118, 1675–1683 (2014). https://doi.org/10.1007/s10973-014-4045-3

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