The Polymer Society of Korea

Abstract

Designing recyclable polymers with controllable depolymerization behavior remains a key challenge in sustainable materials science. In our previous study, density functional theory (DFT) calculations demonstrated that topochemically synthesized polymers with elongated C–C bonds exhibit significantly lower bond dissociation energies (BDEs) than conventional polymers, rationalizing their enhanced depolymerization behavior. In the present study, we extend this computational framework using polymer dimer models with a common backbone and systematically varied substituents to elucidate the relationships among BDE, radical stabilization energy (RSE), and spin population. The results reveal a clear correlation between bond weakening and radical stabilization, indicating thermodynamically favorable radical intermediates. These trends are further supported by spin population analyses, underscoring the critical role of electronic structure effects in governing polymer reversibility.