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

摘要

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.