Kinetic study of Ru III ‐catalyzed polymerization of methylmethacrylate initiated with n ‐butylamine in the presence of carbon tetrachloride by a charge‐transfer mechanism

Ruthenium trichloride (RuCl 3 or Ru III ) catalyzed polymerization of methylmethacrylate (MMA) initiated with n ‐butylamine (BA) in the presence of carbon tetrachloride (CCl 4 ) by a charge‐transfer mechanism has been investigated in a dimethylsulfoxide (DMSO) medium by employing a dilatometric technique at 60°C. The rate of polymerization ( R p ) has been obtained under the conditions [CCl 4 ]/[BA] ⩽ 1 and [CCl 4 ]/[BA] ⩾ 1. The kinetic data indicate the possible participation of the charge‐transfer complex formed between the amine–Ru III complex and CCl 4 in the polymerization of MMA. In the absence of either CCl 4 or BA, no polymerization of MMA is observed under the present experimental conditions. The rate of polymerization is inhibited by hydroquinone, suggesting a free‐radical initiation. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 43: 70–77, 2011