Thermokinetic parameters analysis for 1,1-bis-(tert-butylperoxy)-3,3,5-trimethylcyclohexane at isothermal conditions for safety assessment

Chen, Wei‐Ting; Chen, Wei‐Chun; Hsueh, Kuang-Hua; Chiu, Chi-Tsung; Shu, Chi‐Min

doi:10.1007/s10973-014-3744-0

Cited by 10 publications

(1 citation statement)

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“…The probability of a decomposition reaction during storage and transportation must be assessed; thus, developing simple rules based on reaction kinetic parameters, such as TMR ad , temperature of no return, and SADT, is useful. The approach for determining TMR ad applies the equations with the actual kinetics [15]. However, most reactions are complex.…”

Section: Introductionmentioning

confidence: 99%

Prediction of thermal hazard for TBPTMH mixed with BPO through DSC and isoconversional kinetics analysis

Chen

Shu

2016

J Therm Anal Calorim

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tert-Butyl peroxy-3,5,5-trimethylhexanoate (TBPTMH), generally used as an initiator, can replace tertbutyl peroxybenzoate (TBPB) in polymerization processes. The thermal behavior of TBPTMH added to this reaction was analyzed. Furthermore, we compared the influence on thermal hazards with TBPB and benzoyl peroxide. Through differential scanning calorimetry and isoconversional kinetics analysis, thermokinetic parameters and simulation results, including apparent activation energy (E a ), time to maximum rate under adiabatic conditions (TMR ad ), and selfaccelerating decomposition temperature (SADT), can be used to identify a safer handling environment when TBPTMH is mixed with tert-butyl peroxide. According to DSC thermal curves, the apparent exothermic onset temperature of TBPTMH was from 100 to 124°C, and the heat of decomposition of TBPTMH was from 748.81 to 950.48 J g -1 . E a values as calculated using three methods (Ozawa-Flynn-Wall, Friedman, and ASTM E698) were 122.4, 122.7, and 122.0 kJ mol -1 , respectively. From the point of view of thermal loss prevention, TMR ad and SADT are two crucial safety parameters, which were obtained as 61.3°C under 24 h and 55.0°C, respectively.Keywords Apparent activation energy (E a ) Á Selfaccelerating decomposition temperature (SADT) Á Time to maximum rate under adiabatic conditions (TMR ad ) Á Thermal hazard Á Thermokinetic parameter List of symbols APre-exponential factors (s -1 ) C p Heat capacity (J g K -1 ) D Activation energy correction coefficient (dimensionless) E a Apparent activation energy (kJ mol -1 ) DH d Heat of decomposition (J g -1 ) kReaction rate constant (min -1 ) nReaction order (dimensionless) n i Reaction order of ith stage (dimensionless) R Universal gas constant (8.314 J mol -1 K -1 ) SADT Self-accelerating decomposition temperature (°C) T Absolute temperature (K) T max Maximum temperature of reaction (K) TMR ad Time to maximum rate under adiabatic conditions (h) T 0 Apparent exothermic onset temperature of reaction (K) t Time (s) aDegree of conversion (dimensionless) bHeating rate (°C min -1 ) q Density (kg m -3 ) kThermal conductivity (W m K -1 ) DH d Heat of decomposition (J g -1 ) DT ad Adiabatic temperature rise (°C)

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Section: Introductionmentioning

confidence: 99%