In our efforts to develop high performance post-metallocene olefin polymerization catalysts, Mitsui Chemicals developed highly active phenoxy-imine catalyst (FI catalyst, 1) (ref. 1). Further catalytic developments have led to the discovery of tridentate phenoxy-imine and tetradentate catalysts having an m-quaterphenyl structure. Tridentate phenoxy-imine complex 2 is a highly active olefin (co)polymerization catalyst having a high comonomer incorporating ability (ref. 2). With complex 2, copolymerization of ethylene and propylene proceeds under atmospheric pressure to achieve 59 mol% of propylene content. Tetradentate complex 3 is active for ethylene polymerization at high temperature and production of ultra-high molecular weight polyethylene exceeds Mv 1,000,000 (ref. 3). Complex 4 provides oligomers of ethylene with high levels of vinylic chain ends at high catalytic activity (ref. 3). We discovered that the steric effect of the ether ligand in the m-quaterphenyl structure for complex 4 is crucial for polymer chain propagation. By tuning the ether substituents of complex 4, we obtained polyethylene (Mw= 130,000) with high catalytic activity under atmospheric pressure. Details of the syntheses and characterization of the above complexes and their ligand effects for olefin poly/oligomerization behavior are presented.

Recent developments concerning post-metallocene olefin poly/oligomerization catalysts at Mitsui Chemicals

253rd National Meeting (2017)

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