Late transition metal olefin polymerization catalysts still attract great interest from both academia and industry. Besides their ability to produce novel polymer architectures such as hyperbranched and dendritic polyethylene, a main feature is their higher functional group tolerance compared to their early transition metal counterparts. This tolerance not only enables ethylene polymerization by novel processes such as aqueous emulsion polymerization, but also the production of functionalized polyolefins via direct copolymerization of polar vinyl monomers and non-polar olefins. Currently, the only catalysts able to produce such copolymers are based on Pd(II) but generally suffer from low activity.Ruthenium, on the other hand, has been used for a variety of catalytic reactions involving olefins (i.e. hydrogenations, metathesis) and showed excellent functional group tolerance, making it a seemingly promising candidate. However, Ru based olefin insertion polymerization catalyst are scarce. Our lab has previously demonstrated ethylene polymerization at a Ru(II) center by direct spectroscopic methods. More recently, we disclosed Ru(IV) complexes of the phosphine-disulfonato ligand, which produce linear, semicrystalline polyethylene with one of the highest reported activities for Ru based catalysts. It was further found that the polymerization activity increased with the electron withdrawing character of the ligand.Here we would like to discuss the most recent progress with Ru(IV) polymerization catalysts, including insights into the activation mechanism, copolymerization studies and the development of novel ligand variants.

Phosphine-disulfonato Ru complexes: Synthesis and olefin polymerization study

248th National Meeting (2014)

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