An Oxygen Paradox: Catalytic Use of Oxygen in Radical Photopolymerization

A peculiar radical polymerization reaction is presented in which oxygen serves as a cocatalyst, alongside triethylamine, to provide activation with light in the far-red (690 nm, 3 mW cm⁻²) of the PET-RAFT process in the presence of zinc(II) (2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin) as photocatalyst. Apart from the ability to exert temporal control by switching the light on or off, this system possesses the exciting capability of inducing temporal control by removal or reintroduction of oxygen. Furthermore, this multicomponent catalytic system was typified by controlled polymerizations of various acrylate and acrylamide monomers, which all resulted in well-defined polymers with low dispersity (<1.2). The process displayed excellent living characteristics that were demonstrated through chain extensions and a range of degrees of polymerization (200–1600).