Ruthenium(III) catalysis in polymerization of vinyl monomers by charge-transfer mechanism with aminoalcohols and carbontetrachloride: A kinetic study

The kinetics of ruthenium(III) catalyzed polymerization of vinyl monomers (M) (methyl-, ethyl-, and butylacrylates) by charge-transfer mechanism with aminoalcohols (AA) (namely, ethanol-, diethanol-, and triethanol amines) and carbontetrachloride in dimethylsulfoxide medium have been studied. The rate of polymerization depends on the [CCl4]/[AA] ratio and may be represented as Rp proportional to [M][CCl4](1/2) [Ru3+] (1/2)[AA](1/2), when [CCl4]/[AA] <= 1 and R-p proportional to [M](3/2)[Ru3+](1/2)[AA](1/2), when [CCl4]/[AA] > 1 The rate of polymerization of monomers with each aminoalcohol was found to be in the order R-p (methyl-) > R-p (ethyl-) > R-p (butylacrylate) while that of each monomer with different aminoalcohols was found to be in the order of R-p tertiary > R-p secondary > R-p primary aminoalcohol. The suitable mechanism for the polymerization process consistent with kinetic data has been proposed. (c) 2006 Wiley Periodicals, Inc.