Recent Advances in Controlled Production of Long‐Chain Branched Polyolefins

Abstract Polyolefins, composed of carbon and hydrogen atoms, dominate global polymer production. This stems from the wide range of physical and mechanical properties that various polyolefins can cover. Their versatile properties are largely tuned by chain microstructure, including molar mass distribution, comonomer content, and long‐chain branching (LCB). Specifically, LCB imparts unique characteristics, notably enhanced processability crucial for downstream applications. Tailoring LCB structural features has encouraged academic and industrial efforts, chronicled in this review from a chemistry standpoint. While encompassing post‐reaction modification based traditional methods like peroxide grafting, ionizing beam irradiation, and coupling reactions, the main focus is given to catalyst‐centric strategies and innovative polymerization schemes. The advent of single‐site catalysts—metallocenes and late transition metals catalysts—amplified interest in tailored chemical methods, but the progress in LCB formation flourished via tandem catalytic systems and bimetallic catalysts under controlled reaction conditions. Specifically, the breakthrough in coordinative chain transfer polymerization unveiled a novel avenue for controlled LCB synthesis by sequential chain propagation, transfer, liberation, and enchainment. This short review highlights recent approaches for the production of LCB polyolefins that can provide a roadmap crucial for researchers in academia and industry, steering their efforts towards further advancements in production of tailored polyolefin. This article is protected by copyright. All rights reserved