Visible light-induced controlled/“living” radical polymerization of styrene

Well-defined polystyrene with low polydispersity index having methyl and phenylseleno ( SePh) groups at αand ω-chain ends, respectively, was afforded via a controlled/“living” radical polymerization using a new initiating system: (1-phenylethyl)seleno benzene [1-PESePh]/tert.butyl diphenyl (phenylseleno) silane [PhSeSiR3] and absorbing visible light at room temperature. A novel design initiating living radical polymerization in a catalytic fashion is described. The polymer yields and number average molecular weight (Mn) of the resulting polymer increased with reaction time. Further, a linear relationship was found for a plot of Mn versus polymer yield. These results indicate that this polymerization proceeds through a living radical mechanism. Recently several remarkable methodologies [1–7] have been developed to design macromolecules via living radical polymerization. Among them, the iniferter method discovered by Otsu et al. [8–10] is an effective way to synthesize well-defined polymers [11, 12], which do not polymerize via an ionic mechanism. An iniferter is an initiator, which also functions as chain transfer and/or primary radical terminator.