The Polymer Society of Korea

Abstract

Reversible ring-opening metathesis polymerization (ROMP) of cyclooctene (COE) derivatives is challenging due to their high ring strain energies. Conventional strategies rely on fused bicyclic monomers, limiting molecular design. In this work, we demonstrate efficient reversible ROMP of non-bicyclic COE derivatives through conformational control using geminal tert-butyl and hydroxyl substituents. These tailored monomers show depolymerization efficiencies exceeding 90%, enabling near-quantitative monomer recovery under optimized conditions. Experimental and computational studies reveal that intramolecular OH–π interactions stabilize cyclic monomer conformations, while steric hindrance in the ring-opened polymer state promotes depolymerization. This work establishes a new substituent-driven design strategy for chemically recyclable polymers beyond bicyclic systems.