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

Nature Chemistry volume 6, pages 179187 (2014) | Download Citation

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

    • Anthony Kermagoret
    • , Antoine Debuigne
    • , Christine Jérôme
    •  & Christophe Detrembleur

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The authors declare no competing financial interests.

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Correspondence to Christophe Detrembleur.

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https://doi.org/10.1038/nchem.1850

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