A comparative study of ethylene polymerization by bis(aminotropone) Ti catalysts

A series of titanium aminotropone complexes bearing a pair of chelating [O–N] ligands have been synthesized and used for polymerization of ethylene successfully. Ethylene polymerization reactions were carried out at different conditions using the prepared catalysts. The activities for ethylene polymerization were significantly dependent on the catalyst structure. The polymerization activity increased with increasing of the both monomer pressure and [MAO]:[Ti] ratio. The highest activity of the catalysts was obtained at about 30–40 °C. It was demonstrated that unlike the high performance Ti–FI catalysts, bis(aminotropone) Ti catalysts do not require the presence of steric bulk in close proximity to the oxygen moiety. Introduction of the bulky alkyl substitution next to the oxygen moiety decreased the activity of the catalysts. Density Functional Theory (DFT) studies reveal that the active species derived from these catalysts normally possess higher electrophilicity nature compared with those produced using bis(phenoxy-imine) Ti catalysts (Ti–FI catalysts). Hydrogen was used as the chain transfer agent. The activities of the catalysts were increased with hydrogen concentration to some extent, but the M _v values of the obtained polymers were decreased. Crystallinity and melting point of the obtained polymer were between 42–62% and 102–124 °C, respectively. Higher pressure increased both the crystallinity and the M _v values of the resulting polymers. The catalyst 8a also produced PE with almost narrow polydispersities (1.10–2.55) as is typical for single-site catalysts. However, PDI was broadened by time.