Tracking Chain Populations and Branching Structure during Polyethylene Deconstruction Processes.

Catalytic deconstruction has emerged as a promising solution to valorize polyethylene (PE) waste into valuable products, such as oils, fuels, surfactants, and lubricants. Unfortunately, commercialization has been hampered by inadequate optimization of PE deconstruction due to an inability to either truly characterize the polymer transformations or adjust catalytic conditions to match the ever-evolving product distribution and associated property changes. To address these challenges, a detailed analysis of molar mass distributions and thermal characterization was developed herein and applied to low-density polyethylene (LDPE) deconstruction to enable more thorough identification of polymer chain characteristics within the solids (e.g., changes in molar mass or branching structure). For example, LDPE hydrocracking exhibited comparable rates of polymer chain isomerization and C-C bond scission, and the solids generated possessed a broadened molar mass distribution with a disappearance of a significant fraction of highly linear segments, indicating polymer-structure-dependent interactions with the catalyst. Solids analysis from pyrolysis yielded starkly different results, as the resulting solids were devoid of unreacted polymer chains and had a narrowed molar mass distribution even at short times (e.g., 0.2 h). By tracking the polymeric deconstruction behavior as a function of reaction type, time, and catalyst design, we mapped critical pathways toward PE valorization.