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Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning

Nature Reviews Chemistry volume 2, pages 6–14 (2018)Cite this article

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Abstract

More than 50 years have passed since Ziegler and Natta shared the Nobel Prize in Chemistry for their discovery of olefin polymerization catalysts. The field of metal-catalysed polymerization has since matured, in no small part owing to the development of several high-performance catalysts. Although polymerization research has in many ways been driven by catalyst development, this has often occurred as a result of trial and error discovery of a promising motif, followed by extensive tuning of the steric and electronic properties of the ligand(s) present in the lead complex. Recently, some alternative design strategies have emerged that afforded new classes of olefin polymerization catalysts. This Perspective highlights recently designed catalyst motifs and the novel reactivity patterns they enable. Special attention is given to methods specifically designed for the copolymerization of ethylene with polar-functionalized co-monomers — challenging reactions that showcase these creatively designed catalyst motifs.

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Fig. 1: Mechanism for transition-metal-catalysed ethylene polymerization and copolymerization.
Fig. 2: Polymerization strategies making use of chain shuttling, phase transfer and metal–metal cooperativity.
Fig. 3: Chain-walking polymerization and copolymerization mediated by (α-diimine)methylpalladium complexes.
Fig. 4: Interactions between metal, ligand and substrate designed to overcome the polar monomer problem.
Fig. 5: Controlling the redox state of a catalyst can tune its olefin polymerization behaviour.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC, 51522306 and 21690071).

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  1. CAS Key Laboratory of Soft Matter Chemistry, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, China

    Changle Chen

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Chen, C. Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning. Nat Rev Chem 2, 6–14 (2018). https://doi.org/10.1038/s41570-018-0003-0

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