Olefin Polymerization by Dinuclear Zirconium Catalysts Based on Rigid Teraryl Frameworks: Effects on Tacticity and Copolymerization Behavior

摘要

Toward gaining insight into the behavior of bimetallic catalysts for olefin polymerization, a series of structurally related binuclear zirconium catalysts with bisamine bisphenolate and pyridine bisphenolate ligands connected by rigid teraryl units were synthesized. Anthracene-9,10-diyl and 2,3,5,6-tetramethylbenzene-1,4-diyl were employed as linkers. Bulky Si^iPr_3 and SiPh_3 substituents were used in the position ortho to the phenolate oxygen. Pseudo-C_s and C_2 symmetric isomers are observed for the binuclear complexes of bisamine bisphenolate ligands. In general, binuclear catalysts show higher isotacticity compared to the monozirconium analogues, with some differences between isomers. Amine bisphenolate-supported dizirconium complexes were found to be moderately active (up to 1.5 kg mmol_(Zr)^(–1) h^(–1)) for the polymerization of 1-hexene to isotactically enriched poly-1-hexene (up to 45% mmmm) in the presence of stoichiometric trityl or anilinium borate activators. Moderate activity was observed for the production of isotactically enriched polypropylene (up to 2.8 kg mmol_(Zr)^(–1) h^(–1) and up to 25.4% mmmm). The previously proposed model for tacticity control based on distal steric effects from the second metal site is consistent with the observed behavior. Both bisamine bisphenolate and pyridine bisphenolate supported complexes are active for the production of polyethylene in the presence of MAO with activities in the range of 1.1–1.6 kg mmol_(Zr)^(–1) h^(–1) and copolymerize ethylene with α-olefins. Little difference in the level of α-olefin incorporation is observed between mono- and dinuclear catalysts supported with the pyridine bisphenolate catalysts. In contrast, the size of the olefin affects the level of incorporation differently between monometallic and bimetallic catalysts for the bisamine bisphenolate system. The ratio of the incorporation levels with dinuclear vs mononuclear catalysts decreases with increasing comonomer size. This effect is attributed to steric pressure provided by the distal metal center on the larger olefin in dinuclear catalysts.