AGET ATRP in the Presence of Air in Miniemulsion and in Bulk

The recently developed initiation system, activators generated by electron transfer (AGET), is used in atom transfer radical polymerization (ATRP) in the presence of a limited amount of air. Ascorbic acid and tin(II) 2‐ethylhexanoate are used as reducing agents in miniemulsion and bulk, respectively. An excess of reducing agent consumes the oxygen present in the system and, therefore, provides a deoxygenated environment for ATRP. ATRP of butyl acrylate is successfully carried out in miniemulsion and in the presence of air. During polymerization the radical concentration remains constant. The polymerization reaches over 60% monomer conversion after 6 h, which results in polymers with a predetermined molecular weight $\overline M _{\rm n}$ = 14 000 g · mol−1 and a low polydispersity ($\overline M _{\rm w} /\overline M _{\rm n}$ = 1.23). AGET ATRP of styrene is also successful in bulk in the presence of air, as evidenced by linear semi‐logarithmic kinetics, which leads to polystyrene with an $\overline M _{\rm n}$ of 13 400 g · mol−1 and a low polydispersity index ($\overline M _{\rm w} /\overline M _{\rm n}$ = 1.14). Appearance of miniemulsion before and after the reducing agent ascorbic acid was added (left); and GPC traces representing molecular weights during the AGET ATRP of BA in miniemulsion in the presence of air (right).