Controlled Radical Polymerization of Acrylates Regulated by Visible Light

The controlled radical polymerization of a variety of acrylate monomers is reported using an Ir-catalyzed visible light mediated process leading to well-defined homo-, random, and block copolymers. The polymerizations could be efficiently activated and deactivated using light while maintaining a linear increase in molecular weight with conversion and first order kinetics. The robust nature of the fac -[Ir(ppy) 3 ] catalyst allows carboxylic acids to be directly introduced at the chain ends through functional initiators or along the backbone of random copolymers (controlled process up to 50 mol % acrylic acid incorporation). In contrast to traditional ATRP procedures, low polydispersity block copolymers, poly(acrylate)- b -(acrylate), poly(methacrylate)- b -(acrylate), and poly(acrylate)- b -(methacrylate), could be prepared with no monomer sequence requirements. These results illustrate the increasing generality and utility of light mediated Ir-catalyzed polymerization as a platform for polymer synthesis.