Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

Jian, Zhongbao; Falivene, Laura; Boffa, Giusi; Sánchez, Sheila Ortega; Caporaso, Lucia; Grassi, Alfonso; Mecking, Stefan

Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

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Embargo End Date

2017-10-14

Type

Article

Authors

Jian, Zhongbao
Falivene, Laura

Boffa, Giusi
Sánchez, Sheila Ortega
Caporaso, Lucia

Grassi, Alfonso
Mecking, Stefan

KAUST Department

KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division

Online Publication Date

2016-10-13

Print Publication Date

2016-11-07

Date

2016-10-14

Abstract

A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII-catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers’ different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a π–η3 interaction for the case of VF.

Citation

Jian Z, Falivene L, Boffa G, Sánchez SO, Caporaso L, et al. (2016) Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization. Angewandte Chemie International Edition 55: 14378–14383. Available: http://dx.doi.org/10.1002/anie.201607754.

Acknowledgements

Z.J.is grateful to the Alexander von Humboldt Foundation for a postdoctoral research fellowship and to the University of Konstanz for support within the EU FP7 Marie Curie Zukunftskolleg Incoming Fellowship Programme. Inigo Gçttker-Schnetmann is gratefully acknowledged for helpful discussions.The authors also thank Lars Bolk for GPC and DSC experiments.