Transition Metal-Catalyzed Ternary Polymerization of Olefins

Polyolefins are widely used polymers, with an annual global production of hundreds of millions of tons. Because they are the simplest hydrocarbon polymers, their intrinsic non-polar properties limit further applications. Coordination–insertion copolymerization of an olefin with other monomers, mediated by transition metal catalysts, is the most efficient way to synthesize polar and multi-functionalized polyolefins with enhanced material performance. Previous reviews have primarily focused on the structural design of a specific catalyst or on binary copolymerization of an olefin with a particular comonomer. However, the transition-metal-catalyzed ternary coordination–insertion polymerization of olefin monomers remains scarce. In this contribution, early transition-metal catalysts, such as Ti, Zr, Hf, and V, are employed for the terpolymerization of all-hydrocarbon or non-polar monomers to access advanced polyolefin materials with high performance. By contrast, late transition metal catalysts based on Ni and Pd, as well as rare-earth metal catalysts ligated by Sc and Y, enable the terpolymerization of olefins with a variety of heteroatom-containing monomers. Their strong tolerance empowers the development of polyolefins with multiple functionalities, thereby distinguishing these systems. The catalyst structure, catalytic process, and mechanism studies are summarized, along with the microstructure and functionality of the polymerization products, by classifying the types of termonomers employed.