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Evaluation of thermal decomposition phenomenon for 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane by DSC and VSP2

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Abstract

1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (TMCH), like many organic peroxides (OPs), is generally employed as a polymerization initiator and is also used comprehensively in the manufacturing process. There are two peroxy groups (–O–O–) in TMCH’s structure, so the entropy of TMCH is relatively higher than other OPs. Therefore, TMCH may release enormous amounts of energy when it decomposes and may cause serious accidents, including runaway reaction, fire, explosion, and toxic release. The aim of this study was to appraise the thermokinetic parameters of TMCH, such as heat of decomposition (ΔH d), exothermic onset temperature (T 0), maximum pressure and temperature ( P max and T max ), and other safety parameters by vent sizing package 2 (VSP2) and differential scanning calorimetry (DSC). ΔH d of TMCH is detected by DSC averaging 1103 J g−1, and apparent activation energy (E a) of different mass% of TMCH, such as 20, 25, and 30 mass%, were evaluated as 154.45, 150.07, and 142.98 kJ mol−1, respectively. Furthermore, we applied a novel advanced kinetics software to simulate the thermokinetic parameters of TMCH. According to this study, we can not only grasp the thermal properties and runaway reaction of TMCH, but also build up a safer process design to prevent and mitigate the runaway reaction.

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Abbreviations

A :

Frequency factor (s−1 M1−n)

dα dt −1 :

Conversion rate (dimensionless)

dT dt −1 :

Self-heating rate, reaction rate (°C min−1)

dP dt −1 :

Pressure rise rate (psig min−1)

\( ( {\text{dT}}\,{\text{dt}}^{ - 1} )_{ \hbox{max} } \) :

Maximum self-heating rate (°C min−1)

\( ( {\text{d}}P\,{\text{dt}}^{ - 1} )_{ \hbox{max} } \) :

Maximum pressure rise rate (psig min−1)

E a :

Apparent activation energy (kJ mol−1)

f(α):

Reaction model (dimensionless)

ΔH d :

Heat of decomposition (J g−1)

k :

Reaction rate constant (min−1)

MTSR:

Maximum temperature reached due to the synthesis reaction (°C)

n :

Reaction order (dimensionless)

R :

Gas constant (8.314 J mol−1 K−1)

P max :

Maximum pressure (psig)

SADT:

Self-accelerating decomposition temperature (°C)

T 0 :

Apparent exothermic onset temperature (°C)

T f :

Final temperature (°C)

T max :

Maximum temperature (°C)

T initial :

Initial adiabatic decomposition temperature (°C)

TMR:

Time to maximum rate (min, h, day)

TMRad :

Time to maximum rate under adiabatic conditions (°C)

α :

Degree of conversion (dimensionless)

β :

Heating rate (°C min−1)

Φ :

Thermal inertia (dimensionless)

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Acknowledgements

The authors are indebted to the technical information from the AKTS guide book on this study.

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Authors and Affiliations

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

    Wei-Chun Chen & Yun-Ting Tsai

  2. Department General Education, Chienkuo Technology University, 1, Chiehshou North Rd., Changhua, 500, Taiwan, ROC

    Mei-Li You

  3. Department of Cosmetic Application & Management, St. Mary’s Junior College of Medicine, Nursing and Management, Yilan, 26644, Taiwan, ROC

    Wei-Ting Chen

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

    Chi-Min Shu

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  1. Wei-Ting Chen
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Correspondence to Mei-Li You.

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Chen, WT., Chen, WC., You, ML. et al. Evaluation of thermal decomposition phenomenon for 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane by DSC and VSP2. J Therm Anal Calorim 122, 1125–1133 (2015). https://doi.org/10.1007/s10973-015-4985-2

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  • DOI: https://doi.org/10.1007/s10973-015-4985-2

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