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

Angew Chem Int Ed Engl. 2016 Nov 7;55(46):14378-14383. doi: 10.1002/anie.201607754. Epub 2016 Oct 13.

Authors

Zhongbao Jian¹, Laura Falivene², Giusi Boffa³, Sheila Ortega Sánchez³, Lucia Caporaso⁴, Alfonso Grassi³, Stefan Mecking⁵

Affiliations

¹ Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Universitätsstrasse 10, 78457, Konstanz, Germany.
² Physical Sciences and Engineering, Kaust Catalysis Center, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
³ Department of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano, SA, Italy.
⁴ Department of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano, SA, Italy. lcaporaso@unisa.it.
⁵ Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Universitätsstrasse 10, 78457, Konstanz, Germany. stefan.mecking@uni-konstanz.de.

PMID: 27736020
DOI: 10.1002/anie.201607754

Abstract

A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. Pd^II -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.

Keywords: DFT calculations; insertion; palladium; polyethylene; telechelic polymers.

Publication types

Research Support, Non-U.S. Gov't