The polymerization of ethylene with late transition metal complexes typically provides highly branched amourphous poly(ethylene)s through a chain-walking mechanism, while the chain-straightening polymerization of α-olefins gives semicrystalline polymers. Herein, we report the polymerization of 1-hexene, 1-octene, and 1-dodecene catalyzed by an α-diimine Ni(II) complex in combination with diethylaluminum chloride. The effect of monomer chain length and monomer concentration on the productivity, polymerization “livingness”, selectivity of monomer insertion, and polymer structure/properties is investigated. The polymerization results indicate the possibility of precise microstructure control, depending on the monomer employed and monomer feedstock concentration, which in turn strongly affects the physical polymer properties. Additionally, di- and triblock copolymers were successfully fabricated in an easy, high-yielding route, at room temperature. The synthesis was accomplished through the sequential monomer addition from 1-dodecene and ethylene, without requiring any intermediate separation step. Each block exhibited distinct features from semicrystalline to amorphous, taking advantage of the different mechanism involved in the polymerization of 1-dodecene and ethylene. Investigation on mechanical behavior by uniaxial stretching until failure and step-cycle tensile tests showed that the block copolymers behave as thermoplastic elastomers with different performances depending on the composition, length of the blocks, and crystallinity. We demonstrate that this approach is a route to fabricate thermoplastic elastomers from readily accessible starting materials.

An alternative crosslinking concept for the insulation of HVDC power cables that uses click chemistry is presented.

The most common type of extruded power cable insulation is based on cross-linked polyethylene (XLPE), which cannot be recycled as a thermoplastic material. Hence, thermoplastic insulation materials currently receive considerable attention because they would allow recycling through re-melting. In particular blends of polyethylene (PE) and polypropylene (PP) would be a compelling alternative to XLPE, provided that the poor compatibility of the two polymers can be overcome. Here, we establish an alternative approach that exploits the in situ formation of a PE–PP-type copolymer through reactive compounding. Ternary blends of an ethylene-glycidyl methacrylate copolymer, a maleic anhydride-grafted polypropylene, and up to 70 wt % low-density polyethylene (LDPE) are compounded at 170 °C. Covalent bonds form through reaction between epoxy and carboxyl groups, leading to a PE–PP-type copolymer that shows good compatibility with LDPE. The in situ generated PE–PP copolymer arrests creep above the melting temperature of LDPE, mediated by a continuous network that is held together by PP crystallites. Recyclability is confirmed by reprocessing at 170 °C. Furthermore, the here investigated formulations feature a low direct-current electrical conductivity of ∼4 × 10–14 S m–1 at 70 °C and 30 kV mm–1, on a par with values measured for LDPE and XLPE. Evidently, in situ formation of a PE–PP-type copolymer through reactive compounding is a promising approach that may enable the design of thermoplastic insulation materials for power cables.

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High‐voltage direct‐current power cables are vital for the efficient transport of electricity derived from renewable sources of energy. The most widely used material for high‐voltage power cable insulation – low‐density polyethylene (LDPE) – is usually crosslinked with peroxides, a process that releases unwanted by‐products. Hence, by‐product‐free crosslinking concepts that mitigate the associated increase in electrical conductivity are in high demand. Click chemistry‐type crosslinking of polyethylene copolymer mixtures that contain glycidyl methacrylate and acrylic acid co‐monomers is a promising alternative, provided that the curing reaction can be controlled. Here, we demonstrate that the rate of the curing reaction can be adjusted by tuning the number of epoxy and carboxyl groups. Both dilution of copolymer mixtures with neat LDPE and the selection of copolymers with a lower co‐monomer content have an equivalent effect on the curing speed. Ternary blends that contain 50 wt% of neat LDPE feature an extended extrusion window of up to 170 °C. Instead, at 200 °C rapid curing is possible, leading to thermosets with a low direct‐current electrical conductivity of about 10−16 S cm−1 at an electric field of 20 kV mm−1 and 70 °C. The conductivity of the blends explored here is comparable to or even lower than values measured for both ultraclean LDPE and a peroxide‐cured commercial crosslinked polyethylene grade. Hence, click chemistry curing represents a promising alternative to radical crosslinking with peroxides. © 2019 Society of Chemical Industry

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The here established crosslinking chemistry opens up a by-product free method for rapid curing of epoxy-functionalised polyethylenes.

In recent years it has been introduced a new generation of complexes of transition metals and lanthanides with various ligands containing donor atoms such as P, N, and O (e.g., phosphines, imines, iminopyridines, and ketoimines) that, in combination with MAO, give highly stereoregular polymers (cis-1,4, iso-and syndiotactic; 1,2, iso-and syndiotactic) from various substituted butadienes (i.e., isoprene, 1,3pentadiene, 1,3-hexadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3octadiene, and 5-methyl-1,3-hexadiene). The availability of all these stereoregular polymers has allowed us to have access, via hydrogenation reaction with p-toluenesulfonyl hydrazide, to a whole series of olefin homopolymers and perfectly alternating copolymers which, in some cases, were not obtainable through the simple stereospecific polymerization of the corresponding monomers. In this communication, we report on the synthesis and characterization (by NMR, DSC, GPC, and X-ray) of four perfectly alternating ethylene/2-butene copolymers having different stereoregularity degree, from completely isotactic to predominantly syndiotatctic; in particular, the racemo-di-isotactic ethylene/2-butene copolymer obtained by hydrogenation of diisotactic trans-1,4-poly(2,4-hexadiene) is a novel polymer which was never reported before.