A Quantum-chemical study of the mechanism of formation of styrene polymerization centers under initiation by the ferrocene—benzoyl peroxide system

The mechanism of formation of free polystyrene growth radicals and radicals bound to complexes with ferrocene when polymerization was performed in the presence of the ferrocene—benzoyl peroxide initiating system was studied by quantum-chemical calculations with the use of the PRIRODA program and the PBE/3z method. The calculated structure of the charge transfer complex between ferrocene and benzoyl peroxide was in agreement with the experimental data. The calculated heat effects of possible complex decomposition reactions showed that radical formation easily occurred in the presence of the monomer only. The most favorable energetically scheme of the formation of the active centers of the complex-radical polymerization of styrene, including the intermediate formation of the ferrocene—benzoyloxy radical complex, was suggested.