A strategy is introduced for the synthesis of polyethylene-block-poly(ε-caprolactone) block copolymers by a combination of coordination polymerization and ring-opening polymerization. First, end-hydroxylated polyethylene (PE-OH) was prepared with a one-step process through ethylene/3-buten-1-ol copolymerization catalyzed by a vanadium(III) complex bearing a bidentate [N,O] ligand ([PhNC(CH₃)CHC(Ph)O]VCl₂(THF)₂). The PE-OH was then used as macroinitiator for ring-opening polymerization of ε-caprolactone, leading to the desired nonpolar/polar diblock copolymers. The block structure was confirmed by spectral analysis using ¹H NMR, gel permeation chromatography and differential scanning calorimetry. The unusual topologies of the model copolymers will establish a fundamental understanding for structure–property correlations, e.g. compatibilization, of polymer blends and surface and interface modification of other polymers. © 2014 Society of Chemical Industry

The synthesis of amphiphilic linear-hyperbranched graft-copolymers in a grafting-from approach is reported. The linear polyethylene with terminated hydroxyls, prepared by copolymerization of ethylene and 10-undecen-1-ol, was used as macroinitiator for ring-opening multibranching polymerization of glycidol by a typical slow monomer addition approach. Successful attachment of the hyperbranched grafts to the linear polyethylene backbone was confirmed by ¹H/¹³C NMR, GPC, and TGA. The degree of polymerization and M_w/M_n of hyperbranched grafts were efficiently controlled by temperature, deprotonation ratio as well as the molar ratio of glycidol/hydroxyl (N_glycidol/N_OH). The complicated microstructures caused by unsymmetric glycidol structure were analyzed by DEPT and 2D HSQC spectra, the degree of branching of 0.63–0.66 were calculated, indicating the extent of branch is close to theoretical values. The thermal analysis of linear-hyperbranched copolymers via TGA and DSC is also presented. To our knowledge, this is the first report of a linear-hyperbranched graft-copolymer with a crystalline and nonpolar linear-polyethylene segment. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2146–2154