In this perspective, recent developments on palladium and nickel mediated chain walking olefin polymerization and copolymerization with polar functionalized comonomers are described. First, the chain walking polymerization mechanism is discussed followed by its implications in olefin polymerization and copolymerization. Then, recent advances in catalyst design are provided. Special attention is paid to the influence of ligand structures on the catalytic properties. Subsequently, the applications of these chain walking polymerization catalysts in the synthesis of functionalized hyperbranched polymers and copolymers are summarized. Finally, some recent developments and perspectives on very fast and very slow chain walking polymerization catalysts are discussed.

In the Brookhart type α-diimine palladium catalyst system, it is highly challenging to tune the polymer branching densities through ligand modifications or polymerization conditions. In this contribution, we describe the synthesis and characterization of a series of α-diimine ligands and the corresponding palladium catalysts bearing both the dibenzhydryl moiety and with systematically varied ligand sterics. In ethylene polymerization, it is possible to tune the catalytic activities ((0.77–8.85) × 10⁵ g/(mol Pd·h)), polymer molecular weights (M_n: (0.2–164.7) × 10⁴), branching densities (25–116/1000C), and polymer melting temperatures (amorphous to 98 °C) over a very wide range. In ethylene–methyl acrylate (E–MA) copolymerization, it is possible to tune the catalytic activities ((0.3–8.8) × 10³ g/(mol Pd·h)), copolymer molecular weights (1.1 × 10³–79.8 × 10³), branching densities (30–119/1000C), and MA incorporation ratio (0.4–13.8%) over a very wide range. The molecular weights and branching densities could also be tuned in α-olefin polymerization. The tuning in polymer microstructures leads to significant tuning in polyethylene mechanical properties and the surface properties of the E–MA copolymer.