Benzotriazinyl‐mediated controlled radical polymerization of styrene

The stable free radical polymerization (SFRP) process based on (1,3‐diphenyl‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl), the so‐called ‘Blatter radical’, and several C‐7 substituted derivatives is introduced for the first time for the polymerization of styrene. Polystyrenes characterized by polydispersity indices in the 1.05 ? 1.27 range were obtained in the presence of the Blatter radical and its derivatives containing CF₃, Ph, Fur‐2‐yl and 4‐PhC₆H₄ substituents, while polymerization proceeded either in a non‐controlled manner or in very low polymerization yields in the presence of derivatives containing halogen (Cl, Br, I) substituents. This preliminary investigation, demonstrating the potential use of the Blatter radical and its derivatives in mediated SFRP, creates new opportunities to design and develop radicals to optimize performance in such polymerization processes. © 2013 Society of Chemical Industry