Vinyl polymerization with Fe(III)‐thiourea as initiator system. Part I. General features and kinetics of Fe(ClO4)3‐thiourea reaction

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Abstract
Initiation of polymerization of methyl methacrylate, styrene, and acrylonitrile with the redox system Fe(III)—thiourea has been examined. For the heterophase polymerization any of the ferric salts, such as FeCl3, Fe2(SO4)3, and Fe(ClO4)3 can be used as oxidant, but there is no polymerization in the homogeneous phase when FeCl3 is used as oxidant. It was also observed that Fe(ClO4)3 retards the radical polymerization of styrene, though this salt has hardly any effect on the radical polymerization of methyl methacrylate. Further, the reaction between Fe(ClO4)3 and thiourea was found to be kinetically of second order. The rate is largely influenced by the nature of the solvent. It is concluded that apart from the dielectric constant of the solvents, specific effects like complex formation of Fe(III) with solvents should have a marked influence on the rate of this reaction.

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