Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

Handle URI:
http://hdl.handle.net/10754/623163
Title:
Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization
Authors:
Jian, Zhongbao; Falivene, Laura ( 0000-0003-1509-6191 ) ; Boffa, Giusi; Sánchez, Sheila Ortega; Caporaso, Lucia; Grassi, Alfonso; Mecking, Stefan
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
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.
Publisher:
Wiley-Blackwell
Journal:
Angewandte Chemie International Edition
Issue Date:
14-Oct-2016
DOI:
10.1002/anie.201607754; 10.1002/ange.201607754
Type:
Article
ISSN:
1433-7851
Sponsors:
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.
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/anie.201607754/abstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorJian, Zhongbaoen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorBoffa, Giusien
dc.contributor.authorSánchez, Sheila Ortegaen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorGrassi, Alfonsoen
dc.contributor.authorMecking, Stefanen
dc.date.accessioned2017-04-13T11:50:58Z-
dc.date.available2017-04-13T11:50:58Z-
dc.date.issued2016-10-14en
dc.identifier.citationJian 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.en
dc.identifier.issn1433-7851en
dc.identifier.doi10.1002/anie.201607754en
dc.identifier.doi10.1002/ange.201607754en
dc.identifier.urihttp://hdl.handle.net/10754/623163-
dc.description.abstractA 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.en
dc.description.sponsorshipZ.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.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/anie.201607754/abstracten
dc.subjectDFT calculationsen
dc.subjectinsertionen
dc.subjectpalladiumen
dc.subjectpolyethyleneen
dc.subjecttelechelic polymersen
dc.titleDirect Synthesis of Telechelic Polyethylene by Selective Insertion Polymerizationen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalAngewandte Chemie International Editionen
dc.contributor.institutionChair of Chemical Materials Science, Department of Chemistry, University of Konstanz Universitatsstrasse 10, 78457 Konstanz (Germany)en
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno Via Giovanni Paolo II, 132, 84084 Fisciano, SA (Italy)en
kaust.authorFalivene, Lauraen
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