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A new method was presented for preparing (co-)polyethylene with broad molecular weight distribution (MWD) and high molecular weight employed by the novel heterogeneous Ziegler–Natta catalysts via one-pot strategy. The preparation of these catalysts involved the introduction of alkoxy silane compounds as electron donors. The influences of the electron donors structure, as well as polymerization conditions such as temperature, molar ratio of Al/Ti, ethylene pressure and the concentration of 1-hexene in feed on the polymerization performance for ethylene (co-)polymerization, were investigated. The morphology of the catalyst particles was characterized by SEM and Ti content of these catalysts was characterized by ICP. The GPC results showed that the obtained homopolyethylene and ethylene/1-hexene copolymer had the widest molecular weight distribution up to ca 50 when diethoxy-isopropoxy-(t–butoxy)-silane (ED3) was used as internal electron donor. The 13 C NMR and FT-IR analysis indicated that these catalysts efficiently catalyzed the copolymerization of ethylene with 1-hexene.

Comparison with the conventional Ziegler–Natta catalyst TiCl4/MgCl2 (I), the modified supported Ziegler–Natta catalysts (iso-PentylO)TiCl3/MgCl2 (II) and (BzO)TiCl3/MgCl2 (III) were prepared as efficient catalysts for copolymerization of ethylene with 1-octene. The complexes (II) and (III) were desirable for the production of random ethylene/1-octene copolymers coupled with higher molecular weight, higher comonomer incorporation within copolymer chain and good yield even at high temperature 80 °C and fairly low Al/Ti molar ratio of 100. The effects of catalysts ligands, Al/Ti molar ratio, polymerization temperature, as well as concentration of 1-octene on the catalytic activity, molecular weight and microstructure of the copolymer were investigated in detail. The structure and properties of the copolymers were characterized with 13C NMR, GPC, DSC and WAXD. The kinetic results also indicate that these catalysts (II) and (III) show higher catalytic activity and the produced polymers feature higher molecular weight, because of lower ratio of Ktrm/Kp and Ktra/Kp, and higher ratio of Ktra/Ktrm which indicates that chain transfer to cocatalyst is predominant.