Late Transition Metal Catalysts for the Copolymerization of Olefins and Polar Monomers

The evolution of olefin polymerization catalysis since Karl Ziegler’s and Giulio Natta’s Nobel Prize-winning discoveries in the mid-1950s has involved a prolific interplay of polymer science and organometallic chemistry and led to the development and commercial deployment of catalysts that rival the activities of enzymes and systems, yielding polyolefins possessing structures and physical properties that allow them to be applied in countless applications worldwide. In contrast, commercial processes for the copolymerization of ethylene with polar monomers such as acrylate and vinyl acetate still exclusively employ free radical processes. This chapter reviews recent developments in the catalytic copolymerization of ethylene and these polar comonomers, including well-defined, single-component catalysts capable of copolymerizing (for example) acrylates and vinyl ethers to high molecular weight, linear, random copolymers.