The Polymer Society of Korea

Abstract

Direct functionalization of polymer C–H bonds offers a way to enhance polymers by adding new groups, but preserving chain integrity is difficult. We report a metal-free method for modifying polyethers via light-induced α-C–H amidation. This enables the synthesis of α-amino-functionalized polyethers with unique properties. The reaction follows a polar-radical relay mechanism, allowing selective C–N bond formation at ether α-positions. It minimizes backbone damage and cross-linking under mild conditions. The method shows high selectivity and potential for broader use, including controlled degradation of polyethers and modification of PEG-based materials.