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 su ccessfully carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDP S)/ferric tri(diethyldithiocarbamate) as a novel reverse atom transfer radi cal polymerization initiation system in which DCDPS was a hexa-substituted ethane-type thermal iniferter, DC was a diethyldithiocarbamate group, and n o additional ligands such as nitrogen- or phosphine-based compounds were re quired, The bulk polymerization of methyl methacrylate was carried out at 9 5 degreesC, and that of styrene was carried out at 120 degreesC. Poly(methy l methacrylate) and polystyrene (PSt) with high molecular weights and quite narrow molecular weight distributions (as low as 1.09 for PSt) were obtain ed. H-1 NMR spectroscopy revealed the presence of an alpha-(carbethoxycyano phenyl)methyl group from the initiator and an omega -DC group from the cata lyst in the obtained polymers. Various chain-extension reactions under UV l ight or thermal treatments were successfully conducted to prove the presenc e and efficient reinitiating of the omega -DC group. (C) 2001 John Wiley & Sons, Inc.