Abstract
The initiation of radical polymerization of methyl methacrylate in the presence of benzoyl peroxide-metallocene (Cp2Fe, Cp2ZrCl2, and Cp2TiCl2; (C5Me5)2Fe, (C5Me5)2ZrCl2, and (AcC5H4)(C5H5)Fe) systems is studied. It is shown that a metallocene affects the rate of initiation and the initial rate of polymerization. On the basis of quantum-chemical calculations, a new mechanism of the initiation reaction may be advanced: Namely, the decomposition of benzoyl peroxide proceeds via the stage of complexation with a metallocene, while the nature of a metallocene determines the probability of complexation and decomposition.
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