Scission kinetic model for the prediction of polymer pyrolysis curves from chain structure

Abstract

There is a significant interest in correlating polymer structure with thermal degradation behavior. Thus, polymer pyrolysis curves could be predicted from the chemical structure of the polymer. Recent proposals correlate the kinetic temperature function directly with the chemical structure of the polymer by means of the dissociation energy while assuming a semiempirical first order model for the reaction fraction function. However, first order model lacks physical meaning and it produces significant deviations of the predicted curves, mostly under isothermal conditions. Thus, in this work an upgrade of the method is proposed by using a new random scission kinetic model. The newly proposed kinetic equation has been checked by fitting the experimental data reported by different authors for the thermal pyrolysis of polystyrene. It has been demonstrated that it accounts for the experimental data of polymer degradation under different heating schedule with considerably higher precision than the previously assumed first order kinetics