Kinetics and mechanism of the charge‐transfer polymerization of methyl methacrylate initiated with n ‐butyl amine and carbon tetrachloride catalyzed by palladium dichloride

Abstract We studied the kinetics and mechanism of the charge‐transfer polymerization of methyl methacrylate (MMA) initiated with n ‐butyl amine (BA) and carbon tetrachloride (CCl 4 ) catalyzed by palladium dichloride (PdCl 2 or Pd II ) in a dimethyl sulfoxide medium by using a dilatometric technique at 60°C. The rate of polymerization ( R p ) was a function of [MMA], [BA], [CCl 4 ], and [Pd II ]. The kinetic data indicated a mechanism involving the possible participation of the charge‐transfer complex formed between the {BA–Pd II } complex and CCl 4 or monomer in the polymerization of MMA. In the absence of either CCl 4 or BA, no polymerization of MMA was observed under these experimental conditions. R p was inhibited by hydroquinone; this suggested a free‐radical initiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012