Theoretical study of ethylene polymerization by phenoxy-imine catalyst

Abstract

Reaction mechanisms of ethylene polymerization catalyzed by the phenoxy-imine (FI) and the nickel phenoxyphosphine polyethylene glycol (Ni-PEG) with alkali metals were explored using DFT calculations. For FI catalysts, the effect of group IVB transition metals substitutions was investigated. The trend of calculated activation energies (Ea) at the rate-determining step is Zr < Hf < Ti and is in good agreement with experiments. The effect of ligands of the Ti-FI-based catalysts when changing the parent nitrogen (O, N) to oxygen (O, O), phosphorus (O, P), and sulfur (O, S) ligands on activity was also monitored. The results indicated that the sulfur (O, S) ligand gives the lowest activation energy. Additionally, the reactivity of Ni-phenoxy-imine (Ni-FI)-based catalysts for polyethylene polymerization was studied. Our calculations suggested that the square planar complex of Ni-FI is more reactive than its C2 symmetric octahedral complex. For Ni-PEG(M) catalysts, the trend for activation energies of four Ni-PEG(M) systems is Li < Na < K < Cs, which corresponds to experimentally observed activities. Moreover, the roles of secondary metals in Ni-PEG catalysts in terms of steric, electronic, and electrostatic effects were elucidated. The DFT results suggested that the active catalyst should have strong cooperative metal-metal/metal-ligand interactions and less positive charge on the secondary metal. Finally, to gain insight into the design of the novel Ni-PEG catalysts with alkali-earth metals, the effect of catalyst structure on experimental activity was investigated. This work provides fundamental understandings of the reaction mechanisms for the FI and Ni-PEG(M) catalysts, which could be used for the design and development of catalysts for ethylene polymerization.