Redox polymerization, 3. Kinetics of acrylonitrile polymerization initiated by the redox systems cyanoacetic acid/Mn(III) and 2-butanone/Mn(III) in aqueous sulfuric acid

The kinetics of Polymerization of acrylonitrile initiated by the redox systems cyanoacetic acid/Mn(III) and 2-butanone/Mn(III) were investigated in the temperature range of 30 – 50°C in aqueous sulfuric acid. The kinetics are consistent with the formation of a 1 : 1 complex between the reducing agent and Mn(III), its unimolecular decomposition yielding the initiating radical. Extensive oxidation of the primary radical with exclusively mutual termination of growing radicals accounts for the kinetics of the polymerization. Rate and equilibrium constants as well as thermodynamic parameters were evaluated and their significance is discussed.