Abstract
Due to unique characteristics observed in the classical Ziegler-type vanadium catalysts, design and synthesis of new vanadium complex catalysts for olefin polymerization have been recognized as an attractive target. This chapter summarizes reported examples of vanadium complexes employed as the homogeneous catalyst precursors for olefin polymerization, including recent efforts using (arylimido) vanadium(V) complex catalysts for precise olefin polymerization. Vanadium(III) species are assumed to play an important role as the catalytically active species in olefin polymerization using classical Ziegler-type vanadium catalyst systems. (Imido)(aryloxo)vanadium(V) complexes containing anionic ancillary donor ligands are effective not only for ethylene polymerization but also for ethylene/norbornene copolymerization affording copolymers with uniform distributions. Halogenated Al alkyls (Et2AlCl, EtAlCl2, (isoBu)2Cl, Me2AlCl) were suited as the cocatalyst for ethylene (co)polymerization, affording exceptionally high molecular weight polymers with narrow molecular weight distributions. Both Al cocatalyst and solvent directly affect the activity, comonomer incorporation, probably due to so-called catalyst/cocatalyst nuclearity effect.
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