Synthesis of block copolymers by combination of atom transfer radical polymerization and visible light-induced free radical promoted cationic polymerization

A new synthetic approach for the preparation of block copolymers by mechanistic transformation from atom transfer radical polymerization (ATRP) to visible light-induced free radical promoted cationic polymerization is described. A series of halide end-functionalized polystyrenes with different molecular weights synthesized by ATRP were utilized as macro-coinitiators in dimanganese decacarbonyl [Mn₂(CO)₁₀] mediated free radical promoted cationic photopolymerization of cyclohexene oxide or isobutyl vinyl ether. Precursor polymers and corresponding block copolymers were characterized by spectral, chromatographic, and thermal analyses.