Kinetics of the Ruthenium(III) and Palladium(II) Catalysed Polymerization of Methylmethacrylate by Aminoalcohols in Presence of CCI4

Abstract

Ruthenium(III) and palladium(II) catalysed polymerization of
methylmethacrylate (MMA) with aminoalcohols, viz., ethanolamine
(EA) and diethanolamine (DEA) has been studied in presence of
CCl₄ and in dimethylsulfoxide (DMSO) medium by employing a
dilatometric technique at. 60°C. The rate of polymerization (R_p ) of
MMA is proportional to [MMA], [Aminoalcohol]^1/2, [CCl₄]^1/2 and
{k' + k"[Catalyst]^1/2}, where k' and k" are rate constants for uncatalysed
and catalysed path of polymerization respectively. At
higher CCl₄ concentration when [CCI₄]/[Aminoalcohols] > 1, the
rate of polymerization becomes independent of [CCI₄]. The rate of
polymerization is inhibited by hydroquinone, suggesting a free radical
mechanism. Mechanism involving the charge-transfer complex
between {Aminoalcohol-Catalyst} complex and CCI₄ has been suggested
for the initiation of polymerization of Methylmethacrylate.