Redox polymerization-kinetics of the reaction inititated by the system CH2(CH)2?MN(III) in aqueous H2SO4 and the system CH2(CN)2?MN(OAC)3 in DMF and acetic acid

Polymerization of acrylonitrile and methyl methacrylate by the redox systems propanedinitrile-Mn(III) in aqueous sulfuric acid and propanedinitrile-Mn(OAc)₃ in DMF and glacial acetic acid was investigated in the temperature range 20–40°C. The kinetics are consistent with the formation of an intermediate complex whose irreversible decomposition yields the initiating radical. With both monomers mutual termination predominates. The main difference between aqueous H₂SO₄ and acetic acid compared with DMF lies in the ease of oxidation of the primary radicals by the oxidant. Rate and equilibrium parameters were estimated and their significance discussed.