Abstract
A series of binuclear nickel phenoxyiminato catalysts with different linkers and fluorine substituents were efficiently synthesized. Binuclear nickel catalysts with rigid linkers showed higher catalytic activity and thermal stability in ethylene polymerization and produced polymers with higher molecular weight possibly due to the larger steric hindrance and metal-metal synergistic effect. The introduction of fluorine atoms on the N-terphenyl moity also enhanced polymerization activity and molecular weight of polymer due to the electronic effect of fluorine atoms.
Highlights
Late-transition-metal catalysts have attracted more and more attention due to their tremendous potential for olefin and polar monomers copolymerization[1−6]
We found that microstructure of polyethylene mainly depended on the electronic effect of fluorine atoms
Acid-catalyzed condensation of these terphenylamines with di-salicylaldehyde bridged by rigid xanthene linker afforded desired ligands L4a−L4c in high yields
Summary
Late-transition-metal catalysts have attracted more and more attention due to their tremendous potential for olefin and polar monomers copolymerization[1−6]. These catalysts can produce polyethylene with highly branched structure and poly(α-olefins) with linear structure through a process termed as “chain walking”[7−12]. Branch density and molecular weight of polymers are mainly controlled by remote electron-withdrawing or electron-donating groups attached on the terphenyl moiety. Among those catalysts, fluorinated catalysts displayed extremely high activity and produced polyethylenes with high molecular weight and low branch density.
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