Kinetic scheme and rate constants for methyl methacrylate synthesis occurring via the radical–coordination mechanism

Abstract

Two kinetic schemes of the bulk radical–coordination polymerization of methyl methacrylate initiated by the benzoyl peroxide–ferrocene system are considered from the standpoint of formal kinetics. The most likely kinetic scheme is the one that includes the reactions characteristic of classical radical polymerization and, additionally, reactions of controlled radical polymerization proceeding via the Organometallic Mediated Radical Polymerization mechanism, a reaction generating a coordination active site, and a chain propagation reaction in the coordination sphere of the metal. The temperature dependences of the rate constants for the reactions of this kinetic scheme at temperatures typical of commercial poly(methyl methacrylate) production (313–353 K) have been determined by solving the inverse kinetic problem.