Tunable modalities in polyolefin synthesis via coordination insertion catalysis

Abstract

Metal-catalyzed coordination insertion polymerization is one of the most widely used methods to prepare polyolefins, a broad class of polymers comprising a vast majority of the synthetic materials market. To impart greater control over the polymerization process, chemists have developed innovative strategies to enable catalyst tuning by reaction engineering (e.g., changing temperature, pressure, solvent, etc.) or introducing external stimuli (e.g., redox reagents, light, boranes, or metal cations). This review article will provide an overview of the various tunable modalities employed to regulate the polymerization of olefins by transition metal complexes. We will focus on the unique capabilities and limitations of various approaches and offer our perspective on how externally regulated polymerization could have meaningful impacts on applications and future research.