Polymerization and copolymerization of styrene by Ph2Zn‐metallocene‐MAO initiator systems.

Combined systems including diphenylzinc, Ph₂Zn, a metallocene, and methylaluminoxane, MAO, have been employed to initiate styrene polymerization. These initiator systems have been also used to initiate the copolymerization of styrene with p‐alkylsubstituted styrenes and with α‐olefins. Both polymerization and copolymerization processes depend on the nature of the metallocene included in the initiator system, the presence of Ph₂Zn, the temperature and the solvent used. Titanocenes produced syndiotactic polystyrene, s‐PS, while zirconocenes gave atactic polystyrene, a‐PS, with a certain content, less the 20% of s‐PS. For copolymerizations the conversion to polymer was also influenced by the comonomer nature and its molar proportion in the initial feed, as well as the sort of metallocene, titanocene or zirconocene included.