Reverse atom transfer radical polymerization of vinyl monomers with Fe[SC(S)NEt2]3 alone as the catalyst

The living radical polymerization of methyl methacrylate and styrene was successfully carried out with diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS)/ferric tri(diethyldithiocarbamate) as a novel reverse atom transfer radical polymerization initiation system in which DCDPS was a hexa‐substituted ethane‐type thermal iniferter, DC was a diethyldithiocarbamate group, and no additional ligands such as nitrogen‐ or phosphine‐based compounds were required. The bulk polymerization of methyl methacrylate was carried out at 95 °C, and that of styrene was carried out at 120 °C. Poly(methyl methacrylate) and polystyrene (PSt) with high molecular weights and quite narrow molecular weight distributions (as low as 1.09 for PSt) were obtained. ¹H NMR spectroscopy revealed the presence of an α‐(carbethoxycyanophenyl)methyl group from the initiator and an ω‐DC group from the catalyst in the obtained polymers. Various chain‐extension reactions under UV light or thermal treatments were successfully conducted to prove the presence and efficient reinitiating of the ω‐DC group. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3464–3473, 2001