Redox polymerization, 7. Kinetics of the polymerization of acrylic acid derivatives initiated by the systems cyanoacetic acid/Mn(OCOCH3)3 and ethyl acetoacetate/Mn(OCOCH3)3 in glacial acetic acid†

The kinetics of polymerization of acrylamide, acrylonitrile and methyl methacrylate by the systems cyanoacetic acid/Mn(OCOCH 3 ) 3 as well as ethyl acetoacetate/Mn(OCOCH 3 ) 3 were investigated in glacial acetic acid medium in the temperature range of 25-45°C. Oxidation proceeds through intermediate complex formation between reactants. Competitive complexation of the substrates by Mn(II) leads to retadation of the rates by added manganous ions. Primary radicals from the substrate account for the initiation when acrylamide is used as the monomer, but with acrylonitrile and methyl methacrylate secondary radicals formed by the interaction of the 1:1 complex with monomers account for initiation. In presence of the monomers the retardation due to added manganous ions is absent. Termination in all cases is of the mutual type. Rate and equilibrium constants were evaluated.