Zirconium complexes with versatile β-diketiminate ligands: Synthesis, structure, and ethylene polymerization

A series of zirconium complexes (2c, 2d, 2f, 2g, 2h, 2i) containing symmetrical or unsymmetrical β-diketiminate ligands were synthesized by the reaction of ZrCl4 · 2THF with lithium salt of the corresponding ligand in 1:2 molar ratio. X-ray crystal structures reveal that complexes 2d and 2g adopt distorted octahedral geometry around the zirconium center. These complexes showed moderate activities for ethylene polymerization, when methylaluminoxane (MAO) was used as cocatalyst. The steric and electronic effects of the substituents at the phenyl rings had considerable influence on the catalytic activities of the metal complex, as well as the molecular weights and molecular weight distributions (MWD) of produced polymers. Introduction of electron-withdrawing CF3 group to phenyls in the ligand led to a significant increase of catalytic activities, and complex 2f (p-CF3) exhibited the highest catalytic activity of 7.45 × 105 g PE/mol-Zr · h among the investigated complexes. Complexes 2a–d could produce ultra-high molecular weight polyethylenes (UHMWPE) that were hardly dissolvable in decahydronaphthalene or 1,2-dichlorobenzene under the molecular weight measurement conditions. Nevertheless, polyethylenes with broad MWD could be afforded by complexes 2g–i, which was probably due to the introduction of bulky unsymmetrical ligands leading to the formation of multi active species under polymerization conditions. High-temperature 13C NMR data indicate the linear structure of obtained polyethylenes.

Graphical abstractZirconium complexes bearing symmetrical or unsymmetrical β-diketiminate ligand were synthesized, which could produce polyethylenes with ultra-high molecular weight or broad molecular weight distribution by varying the substituents of β-diketiminate ligand as well as polymerization conditions. It is the first time that the unsymmetrical β-diketiminate ligands were introduced to the zirconium complexes.Figure optionsDownload full-size imageDownload as PowerPoint slide