Disentangled ultrahigh molecular weight polyethylene (dis-UHMWPE) has excellent processability but can be achieved under extreme conditions. Herein, we report ethylene polymerization with the binuclear half-sandwich scandium complexes C1-Sc2 and C2-Sc2 to afford UHMWPE. C1-Sc2 bearing a short linker shows higher activity and gives higher molecular weight PEs than C2-Sc2 containing a flexible spacer and the mononuclear Sc1 . Strikingly, all UHMWPEs isolated from C1-Sc2 under broad temperature range (25-120 °C) and wide ethylene pressures (2-13 bar) feature very low degree of entanglement as proved by rheological test, DSC annealing study and SEM. These dis-UHMWPEs are facilely mediated solid-state-process at 130 °C and their tensile strength and modulus reach up to 149.2 MPa and 1.5 GPa, respectively. DFT simulations reveal that the formation of dis-UHMWPE is attributed to the binuclear synergic effect and the agostic interaction between the active center and the growing chain.
Keywords: Binuclear Complex; Coordination Polymerization; Rare-Earth Metal; Synergic Effect; dis-UHMWPE.
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