Radical Ring-Opening Polymerization of N-(Malonyloxy)phthalimide-Functionalized Vinylcyclopropane: Tuning Material Property via Selective Decarboxylation†

Abstract

Post-polymerization modification provides an important approach to tuning the material properties of obtained polymers. In this work, we demonstrated a rational design of novel vinylcyclopropane monomer bearing a pendant N-hydroxylphthalimide redox ester, and explored its radical ring-opening polymerization behavior under visible-light conditions. Photochemical decarboxylation of resulted polymer provided unique access to poly(vinylcyclopropane) bearing single ester group in each repeating unit. This decarboxylative modification has greatly reshaped the thermal and mechanical properties, converting a glassy polymer into a soft, ductile, and rubber-like material.