A Highly Active Iron-Based Catalyst System for the AGET ATRP of Styrene.

The atom transfer radical polymerization of styrene using activators generated by electron transfer (AGET ATRP) has been carried out in bulk in a limited amount of air at 110 °C, using 1,3,5-(2'-bromo-2'-methylpropionato)benzene (BMPB) as an initiator and FeCl(3)  · 6H(2) O/tris(3,6-dioxaheptyl) amine (TDA-1)/ascorbic acid (VC) as a novel Fe(III) -mediated catalyst system. The results of the polymerizations demonstrate the features of 'living'/controlled free-radical polymerization, such as the number-average molecular weights being close to their corresponding theoretical values and increasing linearly with monomer conversion, and narrow molecular weight distributions ($\overline M _{\rm w} /\overline M _{\rm n}$ = 1.18-1.26). The end functionality of the obtained polymers was confirmed by (1) H and (13) C NMR spectra as well as a chain-extension reaction.