Measurement and modeling of peroxides half-life: A thermo-kinetic approach

Half-life values of organic peroxides at elevated temperature conditions are important in characterizing the reactivity and are often available in literature or through vendors. However, there is often lack of details/accuracy on methods used to obtain these values, as well as differences in methods across vendors and publications, thus resulting in discrepant reactivity profile. To address this, a method involving calorimetric experiment and thermo-kinetic modeling was developed. The current approach was applied on five peroxides samples to obtain kinetic parameters and estimate their half-life in the temperature range of interest. The measurements were performed by DSC under non-isothermal conditions on the dilute peroxide solutions (∼0.12 M in mineral oil) and the data were kinetically treated according to three model-based and one model-free kinetic equations. A very good agreement was found between the half-life calculated by all kinetic methods, but significant differences were noticed with the kinetic parameters reported in literature. Additionally, the obtained half-life results, based on non-isothermal measurements developed kinetic models, were validated through isothermal calorimetric testing. Given the accuracy and robustness of our results, the current method can be applied to estimate half-life of organic peroxides at elevated temperature conditions.