The Polymer Society of Korea

Abstract

C–H functionalization of polymers enables direct incorporation of new functional groups into polymer backbones, offering opportunities for upcycling commodity polymers. However, achieving selective functionalization while preserving polymer properties and preventing structural deformation remains challenging. Here, we report a transition metal-free post-functionalization for polyethers via photoinduced α-C–H amidation. This method provides access to previously inaccessible α-amino polyethers with properties distinct from the parent polymers. Through a polar-radical relay mechanism, C–N bonds are selectively introduced into the polyether backbone while suppressing side reactions. Under mild conditions, this approach shows high site selectivity at the ethereal α-position, enabling controlled macromolecular post-functionalization. The strategy also shows potential for amidative degradation of commodity polymers and transformation of PEG networks.