(451c) Detailed Mechanistic Modeling of High-Density Polyethylene Pyrolysis: Low Molecular Weight Product Evolution

A detailed, mechanistic model for high-density polyethylene pyrolysis was created based on the modeling framework developed in our previous work. This modeling framework has been previously applied to polypropylene pyrolysis, polystyrene pyrolysis, mixed polypropylene and polystyrene pyrolysis, and living free radical polymerization. In this work the model of polyethylene pyrolysis was used to study the time evolution of low molecular weight products formed. Specifically, the role that unzipping, backbiting, and random scission reaction pathways play in the evolution of low molecular weight species was probed. The model tracked 151 species and included over 11,000 reactions. Rate parameters were adapted from our previous work, literature values, and regression against experimental data. The model results were found to be in excellent agreement with experimental data for the evolution of condensable low molecular weight products. The time evolution curves of specific low molecular weight products indicated that the random scission pathway was important for all species, while the backbiting pathway played a complementary role. Net rate analysis was used to further elucidate the competition between the pathways. Net rate analysis of end-chain radicals showed that the unzipping pathway was not competitive with the other pathways, as expected based on experimental yields of ethylene. The random scission pathway was found to be controlling, with the backbiting pathway playing a more minor role for product formation. By comparing the net rates for formation of specific mid-chain radicals via intramolecular hydrogen shift reactions, the contribution of the backbiting pathway was shown to vary, with radicals formed via the most facile x,x+4 intramolecular hydrogen transfer reactions being favored.