Redox polymerization-kinetics of the reaction inititated by the system CH<SUB>2</SUB>(CH)<SUB>2</SUB>-MN(III) in aqueous H<SUB>2</SUB>SO<SUB>4</SUB> and the system CH<SUB>2</SUB>(CN)<SUB>2</SUB>-MN(OAC)<SUB>3</SUB> 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&#176;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

Polymerization of acrylonitrile initiated by the redox system 2,2'-thiodiethanol/Ce<SUP>4+</SUP> in aqueous sulfuric acid

The polymerization of acrylonitrile initiated by the redox system 2,2'-thiodiethanol/Ce4+ in dilute sulfuric acid was investigated in the temperature range of 15-25&#176;C. Oxidation of the substrate in the absence of the monomer has also been studied. The reaction involves the formation of an intermediate complex between the metal ion and the protonated species of the reductant, whose decomposition gives rise to the initiating free radicals. Multual interaction of the growing macroradicals accounts for the termination of polymerization. A suitable kinetic scheme has been proposed and rate and equilibrium constants evaluated

Redox polymerization: kinetics of polymerization of acrylonitrile initiated by the system 2,2'-thiodiethanol/trichloroaquobipyridylmanganese(III) in dilute sulfuric acid

The kinetics of polymerization of acrylonitrile and methyl methacrylate initiated by the redox system 2,2'-thiodiethanol/trichloroaquobipyridylmanganese(III) have been investigated in the temperature range 20-35&#176;C in dilute sulfuric acid. The oxidation of the substrate in the absence of monomer has also been studied. A third-order reaction involving the complex, the substrate, and H+ leads to the production of primary radicals which initiate polymerization of the monomers. The primary radicals are more reactive towards methyl methacrylate than towards acrylonitrile. The termination of polymerization with both monomers is by mutual interaction between the growing radicals. A suitable kinetic scheme has been proposed, and the rate constants evaluated