Initial Stages of Pyrolysis of Polyethylene

Combustion and flammability of plastics are important topics of practical interest directly related to fire safety and recycling of polymeric materials; pyrolysis of the solid is the initial step of its combustion. One of the main ways to study such complicated processes is through detailed mechanistic modeling, in which the process is represented by a set of many elementary reactions. Mechanistic modeling of combustion of plastics is considerably hindered by the lack of necessary kinetic data. In virtually all existing models of polymer pyrolysis the majority of kinetic data used are derived from the corresponding gas phase values of smaller species. The use of gas phase rate constants is, generally, not justified without an experimental justification.;In the first part of the work the influence of condensed phase on the rate of scission of a carbon-carbon bond (the reaction that initiates pyrolysis and combustion) in polyethylene (PE) was studied using the method of Reactive Molecular Dynamics (RMD). A method based on a two-step kinetic mechanism was developed to decouple the cage effect from the kinetics of the reaction under study. It was observed that under the conditions of condensed phase the rate constant of C-C bond scission in PE decreased by an order of magnitude compared to that obtained in vacuum. It was also shown that under the conditions of polymer melt the rate constant does not depend on the length of the polymer chain.;In the second part of the work the kinetics of liquid phase and gas phase products of PE pyrolysis were studied experimentally using Gas Chromatography and Nuclear Magnetic Resonance. Based on the assumption of applicability of gas phase kinetic data for C-C scission reaction and beta-scission reaction under the conditions of polymer melt, rate constants of hydrogen transfer, radical addition to double bonds, and radical recombination were determined via kinetic modeling of the experimental results. The obtained values of the rate constants were found to be in reasonable agreement with the constants of similar reactions of smaller molecules in the gas phase.