Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries

A novel route for the synthesis of poly(ethylene glycol)-b--polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)-catalyzed alkyne-azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one-pot procedure under near-visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mol(-1) and a polydispersity index of 1.20.