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Abstract: The spherical MgCl2 supports treated by methylaluminoxane (named MAO-supports) were prepared using MgCl2·2.56C2H5OH adducts as support material subjected to elimination of EtOH by thermal dealcoholization treatments. Then bis(phenoxy-imine) zirconium complex, bis-[N-(3-tert-butylsalicylidence)cyclohexylaminato] zirconium(IV) dichloride (1), was directly impregnated onto these MAO-supports. ICP, EDX, GC, N2-BET, IR and XRD analyses indicated that the texture of the supports and MAO-supports, the elements on solid catalysts, and so on, were greatly relied on dealcoholization temperature. Meanwhile, it was also found that the activities of the supported catalysts for ethylene polymerization and the properties of resultant polymers were strongly dependent on dealcoholization temperature. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling. [Copyright &y& Elsevier]

Abstract: Trialkylaluminums as cocatalysts for bis(phenoxy-imine)Zr complexes, bis[N-(3-tert-butylsalicylidene)-anilinato]zirconium dichloride (1) and bis[N-(3-tert-butylsalicylidene)-cyclohexylaminato]zirconium dichloride (2), are investigated for ethylene polymerization without MAO or Ph3CB(C6F5)4. The effects of alkylaluminums, Al/Zr molar ratio, polymerization temperature and time as well as the comonomer 1-hexene on polymerization performance are examined. In appropriate range of Al/Zr molar ratio, the catalyst system bis(phenoxy-imine)Zr complex/trialkylaluminum shows high activity for ethylene polymerization, which approximates to bis(phenoxy-imine)Zr complex/MAO system. Their catalytic activities depend on not only the nature, but also the amount, of the trialkylaluminum. Both the molecular weights and the polydispersities (M w/M n) of PEs produced by 1 with Et3Al, He3Al, or Me3Al are higher than those with MAO. The nature, rather than the amount, of alkylaluminum determines the M w and the polydispersity of polymer in polymerization with the same complex. Unexpectedly, M w of the polyethylenes produced with complex 1/triethylaluminum increases with polymerization time. The catalyst system bis(phenoxy-imine)Zr complex/trialkylaluminum has low capacity of copolymerization. [Copyright &y& Elsevier]

Hollow polyethylene spheres were achieved from solution-based ɑ-diimine nickel catalyst system with morphological controllable one-step synthesis. • Homogenous ɑ- diimine nickel complexes often produce bulk viscous polyethylene. • Spherical hollow polyethylene produced by coordination dispersion polymerization. • Tri-nuclear nickel complex show high activity for ethylene polymerization. In this paper, ɑ-diimine nickel catalyst without immobilization was successfully used for one-step synthesis of spherical hollow polyethylene particles at mild condition (1.0 MPa, 25 °C) by conducting coordination dispersion polymerization. It was found 2-methyl-2-pentanol (MP) played a key role in the formation of the unusual hollow particular morphology. By varying the addition amount of MP, changing the bulky groups of alkyl aluminum, and adjusting the concentration of nickel catalyst, the particle size was finely tuned. A plausible mechanism was proposed to interpret the formation of these polyethylene hollow particles. [ABSTRACT FROM AUTHOR]