Abstract
Water and alcohols were employed as solvents for the living radical polymerization of methyl methacrylate (MMA) with the R−X/RuCl2(PPh3)3 initiating systems in the presence and absence of Al(Oi-Pr)3 at 80 °C (initiator R−X: PhCOCHCl2, CCl3Br). These Ru(II)-based systems indeed led to living suspension polymerization even in such protonic solvents to give polymers with controlled molecular weights and narrow molecular weight distributions (Mw/Mn = 1.1−1.3). The living polymerizations in water proceeded faster than those in toluene, and additives such as Al(Oi-Pr)3 were not necessarily required for the polymerization to occur. Especially, the PhCOCHCl2/RuCl2(PPh3)3 initiating system gave high molecular weight poly(MMA) (Mn ∼ 105) with narrow molecular weight distributions (Mw/Mn ∼ 1.1) in water even without Al(Oi-Pr)3. Similar Ru(II)-mediated living processes were feasible in such alcohols as methanol, isobutyl alcohol, and tert-amyl alcohol under similar conditions. The success of these living suspen...
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