Catalytic and inhibiting effects of ferrocene on the bulk radical–coordination polymerization of methyl methacrylate from the standpoint of formal kinetics

Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured

“…Based on experimental and theoretical studies of classical radical polymerization, − on experimental studies − of the kinetics of radically initiated polymerization processes in the presence of metallocenes and molecular characteristics of the resulting polymers, as well as studies devoted to theoretical quantum chemical ,− and kinetic − modeling of these processes, it was concluded that two channels of polymer chain formation exist concurrently in the polymerization under consideration, the radical and the coordination channels; therefore, it can be called radical coordination polymerization. During the polymerization of methyl methacrylate in the presence of benzoyl peroxide and ferrocene (compared to the polymerization of methyl methacrylate in the presence of benzoyl peroxide only) the following was found: (1) the molecular weight of the resulting poly­(methyl methacrylate) decreases, and at the same time, the average molecular weights of the polymer increases with growing conversion of methyl methacrylate − (which is observed in processes with reversible chain deactivation); (2) the proportion of syndiotactic triads in the composition of poly­(methyl methacrylate) increases (which indicates to the course of chain coordination propagation reactions); (3) poly­(methyl methacrylate) is obtained, which is capable to act as a macroinitiator with constant activity while adding new portions of a monomer .…”