Preparation of new FI-type catalyst for polymerization of ethylene

Abstract

AbstractA new FI-type Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)- anthracylaminato]zirconium(IV) dichloride was found to display a moderate ethylene polymerization activity of 42×104 g PE/mmol Zr. h with a viscosity average molecular weight (Mv) of 56×104 at the monomer pressure of 4 bars and temperature of 30 °C. HOMO (the highest occupied molecular orbital) and LUMO (the lowest unoccupied molecular orbital) energy level of the anionic phenoxyimine ligands, were calculated using HF/6-31G method. Plurality of the fused aromatic rings on the catalyst structure decreased the energy gap between the HOMO and LUMO, but could not increase the activity. The highest activity of the catalyst was obtained at about 30 °C following a sharp decrease at higher temperature. The catalyst showed the high activity at about [Al]:[Zr]=80000:1 molar ratio and further addition did not affect the activity of the catalyst. Experimental results revealed that low HOMO energy level is not a necessity to reach high activity of the catalyst. Despite low HOMO energy level, the prepared catalyst displayed moderate polymerization activity. Either the activity of the catalyst or the viscosity average molecular weight of the obtained polymer was affected by the hydrogen concentration slightly. However, activity of the catalyst showed higher sensitivity to amount of hydrogen and increased with increasing the hydrogen concentration. Higher monomer pressure increased productivity, crystallinity and the Mv values of the resulting polymer. Some specification of the obtained polymer was studied.