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Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

Nature Chemistry volume 6, pages 179–187 (2014)Cite this article

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Abstract

The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

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Figure 1: OMRP of ethylene with polar monomers.
Figure 2: Dependence of EVA Mn (top, filled symbols), molar-mass distribution (Mw/Mn, bottom, filled symbols) and Fethylene (open symbols) on VAc conversion for copolymerization of VAc and ethylene.
Figure 3: NMR characterization of random EVAs.
Figure 4: General strategy and SECs for the synthesis of EVA-containing diblock-like and symmetrical triblock-like copolymers at 40 °C.
Figure 5: Characterization of radical species by ESR spectroscopy.

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Acknowledgements

The authors are grateful to the Fonds National de la Recherche Scientifique (FRS-FNRS) and to the Belgian Science Policy for financial support within in the frame of the Interuniversity Attraction Poles Programme (PAI VI/27)–Functional Supramolecular Systems for financial support. A.D. and A.K. are grateful for funding from the University of Liege via the Fonds Speciaux pour la Recherche – Credits de Demarrage. C.D. thanks the FRS-FNRS for funding the MIS research project ‘Organocobalt as a clean source of radicals’. A.D. and C.D. are FRS-FNRS Associate Researcher and Research Director, respectively. The authors also thank G. Cartigny, C. Dannemark, C. Malherbe, C. Damblon and P. De Tullio for their skilful assistance. The authors also thank I. German for his help in editing the manuscript, and C. Lepot for providing a nice proposal for potential cover material.

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  1. Chemistry Department, Center for Education and Research on Macromolecules, University of Liège, Sart-Tilman, B6a, Liège, 4000, Belgium

    Anthony Kermagoret, Antoine Debuigne, Christine Jérôme & Christophe Detrembleur

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Kermagoret, A., Debuigne, A., Jérôme, C. et al. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization. Nature Chem 6, 179–187 (2014). https://doi.org/10.1038/nchem.1850

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