NEt3-Triggered Synthesis of UHMWPE Using Chromium Complexes Bearing Non-innocent Iminopyridine Ligands

Chromium complexes bearing non-innocent iminopyridine ligands were investigated as precatalysts for the polymerization of ethylene using different aluminum cocatalysts and Lewis base NEt3 as additive. Beyond confirming the key role of the chromium to ligand synergy in accessing the active complex, other factors that play a crucial role are (i) the nature of the aluminum activator that influences the ion pair generated, (ii) the presence of the additive that boosts the synthesis of UHMWPE with narrow and unimodal molecular weight distribution even at 40 °C, and (iii) the polymerization temperature that affects the polymerization catalysis and the polymer molecular weight. UV-vis-NIR and Fourier transform infrared (FT-IR) spectroscopic techniques have been applied to inspect the activation process and to understand the mode of action by which NEt3 affects the catalytic conversion of ethylene. NEt3 interacts with the aluminum cocatalyst (rather than with the chromium complex) to form an Et3N-AlRx adduct, thus affecting the catalytic ion pair.