Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

Abstract

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.