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Kinetic and thermal safety analysis for tert-butyl peroxy-3,5,5-trimethylhexanoate by advanced calorimetric technology

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Abstract

Thermal stability parameters were evaluated for the decomposition reaction of tert-butyl peroxy-3,5,5-trimethylhexanoate (TBPMH), a free-radical initiator, by differential scanning calorimetry. According to the results, the apparent exothermic onset temperature, heat of decomposition, and time to maximum rate under adiabatic conditions of TBPMH were 103.0 °C, −924.0 kJ mol−1, and 9.81 min (at 90.0 °C), respectively. A kinetic model was also established under different nonisothermal conditions to evaluate the kinetic behavior of TBPMH by model-free technique and model-fitting method. The self-accelerating decomposition temperature (SADT) was calculated and was similar to that reported in the literature; the SADT values corresponding to various package sizes were also calculated, and an increase in mass caused a drop in SADT. These results can provide a solution to prevent runaway reactions during the storage and transportation of TBPMH, and the applied technique can be a substitute for the complicated procedures and large-scale experiments inherent in traditional analysis methods, thereby preventing process thermal accidents, environmental pollution, and energy depletion.

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Abbreviations

A :

Pre-exponential factor (s−1)

C :

Constant number (dimensionless)

C p :

Specific heat capacity (J g−1 K−1)

C p,c :

Test cell-specific heat capacity (J g−1 K−1)

C p,s :

Sample-specific heat capacity (J g−1 K−1)

dα/dt :

Conversion rate (s−1)

E a :

Apparent activation energy (kj mol−1)

f(α):

Function of degree of conversion (dimensionless)

g :

Geometry factor (dimensionless)

k :

Reaction rate constant (dimensionless)

M c :

Test cell mass (mg)

M s :

Sample mass (mg)

MTSR:

Maximum temperature of synthesis reaction (°C)

N :

Reaction order (dimensionless)

n i :

Reaction order of ith stage (dimensionless)

r :

Correlation coefficient, −1.0 to 1.0 (dimensionless)

R :

Gas constant (8.314 J K−1 mol−1)

R 2 :

Coefficient of determination 0.0–1.0 (dimensionless)

SADT:

Self-accelerating decomposition temperature (°C)

T :

Absolute temperature (K)

T 0 :

Apparent exothermic onset temperature (°C)

T f :

Final temperature (°C)

T max :

Maximum reaction temperature (°C)

TMRad :

Time to maximum rate under adiabatic conditions (min)

T P :

Peak temperature (°C)

T :

Time (s)

x :

Radius of package (m)

y(α):

Function to define the kinetic model for the model-fitting method (dimensionless)

z :

Autocatalytic constant (dimensionless)

α :

Degree of conversion (dimensionless)

α max :

Maximum point at function y(α) (dimensionless)

α p :

Maximum degree of conversion at specific heat flow (dimensionless)

β :

Heating rate (°C min−1)

ρ :

Density (kg m−3)

λ :

Thermal conductivity (W m−1 K−1)

Φ :

Thermal inertia (dimensionless)

∆H d :

Heat of decomposition (J g−1)

∆T ad :

Adiabatic temperature rise (°C)

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Authors and Affiliations

  1. Key Laboratory of Western Mine Exploitation and Hazard Prevention of Ministry of Education, College of Safety Science and Engineering, Xi’an University of Science and Technology (XUST), 58, Yanta Mid. Rd., Beilin Zone, Xi’an, 710054, Shaanxi, China

    Yi Yang & Chi-Min Shu

  2. School of Chemical Engineering and Technology, Xi’an Jiaotong University, 28, Xianning West Rd., Xi’an, 710049, Shaanxi, China

    Yun-Ting Tsai

  3. Center for Process Safety and Industrial Disaster Prevention, School of Engineering, National Yunlin University of Science and Technology, 123, University Rd., Sec. 3, Douliou, 64002, Yunlin, Taiwan, ROC

    Chen-Rui Cao & Chi-Min Shu

Authors
  1. Yi Yang
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  3. Chen-Rui Cao
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Correspondence to Chi-Min Shu.

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Yang, Y., Tsai, YT., Cao, CR. et al. Kinetic and thermal safety analysis for tert-butyl peroxy-3,5,5-trimethylhexanoate by advanced calorimetric technology. J Therm Anal Calorim 127, 2253–2262 (2017). https://doi.org/10.1007/s10973-016-5778-y

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  • DOI: https://doi.org/10.1007/s10973-016-5778-y

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