Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

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

doi:10.1002/anie.201607754

Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

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

Physical Sciences and Engineering

Research output: Contribution to journal › Article › peer-review

69 Scopus citations

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.

Original language	English (US)
Pages (from-to)	14378-14383
Number of pages	6
Journal	Angewandte Chemie International Edition
Volume	55
Issue number	46
DOIs	https://doi.org/10.1002/anie.201607754 https://doi.org/10.1002/ange.201607754
State	Published - Oct 14 2016

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@article{459e4dcaf0d9440e8a63b81fa0dd26d0,

title = "Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization",

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{\textquoteright} 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.",

author = "Zhongbao Jian and Laura Falivene and Giusi Boffa and S{\'a}nchez, {Sheila Ortega} and Lucia Caporaso and Alfonso Grassi and Stefan Mecking",

note = "KAUST Repository Item: Exported on 2020-10-01 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 G{\c c}ttker-Schnetmann is gratefully acknowledged for helpful discussions.The authors also thank Lars Bolk for GPC and DSC experiments.",

year = "2016",

month = oct,

day = "14",

doi = "10.1002/anie.201607754",

language = "English (US)",

volume = "55",

pages = "14378--14383",

journal = "Angewandte Chemie International Edition",

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publisher = "John Wiley and Sons Ltd",

number = "46",

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TY - JOUR

T1 - Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

AU - Jian, Zhongbao

AU - Falivene, Laura

AU - Boffa, Giusi

AU - Sánchez, Sheila Ortega

AU - Caporaso, Lucia

AU - Grassi, Alfonso

AU - Mecking, Stefan

N1 - KAUST Repository Item: Exported on 2020-10-01 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.

PY - 2016/10/14

Y1 - 2016/10/14

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/623163

UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.201607754/abstract

UR - http://www.scopus.com/inward/record.url?scp=84993972089&partnerID=8YFLogxK

U2 - 10.1002/anie.201607754

DO - 10.1002/anie.201607754

M3 - Article

C2 - 27736020

SN - 1433-7851

VL - 55

SP - 14378

EP - 14383

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 46

ER -

Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

Abstract

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CCDC 1063885: Experimental Crystal Structure Determination : (2-(bis(2-methoxyphenyl)phosphanyl)benzene-1-sulfonato)-(1-(furan-2-yl)ethan-1-ido)-palladium benzene solvate

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Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

Abstract

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Datasets

CCDC 1063885: Experimental Crystal Structure Determination : (2-(bis(2-methoxyphenyl)phosphanyl)benzene-1-sulfonato)-(1-(furan-2-yl)ethan-1-ido)-palladium benzene solvate

Cite this