High-throughput computational analysis of kinetic barriers to ring-closing depolymerization for aliphatic polycarbonates

Abstract The chemical reversion of polymers via ring-closing depolymerization (RCD) to their monomeric constituents is a highly promising avenue to enable end-of-life recycling and reuse. However, most reported systems using RCD revolve around bespoke monomer designs to facilitate facile depolymerization, and there exists relatively few investigations into the influence of functional groups on the ability of a particular monomer to cleanly undergo depolymerization. Here, we perform computational investigations into the energy barriers for RCD of 6-membered aliphatic carbonates in different solvents. The results corroborate trends observed in prior experimental studies, validating the utility of computational investigations towards understanding RCD. Experimental evaluation of the thermal depolymerization in two of the studied polycarbonates confirmed their ability to undergo RCD. Overall, this work highlights the advantage of high-throughput energy barrier computations to provide meaningful insight into broad reactivity trends that would be highly laborious to access experimentally.