Effect of Activator and Outgoing Ligand Nature on the Catalytic Behavior of Bis(phenoxy-imine) Ti(IV) Complexes in the Polymerization of Ethylene and Its Copolymerization with Higher Olefins

Svetlana Ch Gagieva; Kasim F Magomedov; Vladislav A Tuskaev; Vyacheslav S Bogdanov; Dmitrii A Kurmaev; Evgenii K Golubev; Gleb L Denisov; Galina G Nikiforova; Maria D Evseeva; Daniele Saracheno; Mikhail I Buzin; Pavel B Dzhevakov; Viktor I Privalov; Boris M Bulychev

doi:10.3390/polym14204397

Effect of Activator and Outgoing Ligand Nature on the Catalytic Behavior of Bis(phenoxy-imine) Ti(IV) Complexes in the Polymerization of Ethylene and Its Copolymerization with Higher Olefins

Polymers (Basel). 2022 Oct 18;14(20):4397. doi: 10.3390/polym14204397.

Authors

Svetlana Ch Gagieva¹, Kasim F Magomedov¹, Vladislav A Tuskaev^{1

2}, Vyacheslav S Bogdanov², Dmitrii A Kurmaev¹, Evgenii K Golubev^{2

3}, Gleb L Denisov², Galina G Nikiforova², Maria D Evseeva¹, Daniele Saracheno^{1

2}, Mikhail I Buzin², Pavel B Dzhevakov¹, Viktor I Privalov⁴, Boris M Bulychev¹

Affiliations

¹ Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russia.
² A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia.
³ Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, Profsoyuznaya Str., 70, 117393 Moscow, Russia.
⁴ Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31, Leninsky Prospect, 119991 Moscow, Russia.

Abstract

A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations Et_nAlCl_3-n + Bu₂Mg and iBu₃Al + [Ph₃C]⁺[B(C₆F₅)₄]^-) on the catalytic activity and properties of the resulting polymers was studied. It was found that Ti-Fi complexes, despite the nature of the outgoing ligands (Cl or iPrO) in the presence of Al/Mg activators, effectively catalyze the polymerization of ethylene (with the formation of UHMWPE); copolymerization of ethylene with 1-octene (with the formation of ultra-high molecular weight copolymers); and the ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene (with the formation of polyolefin elastomers). It has been shown that Zr-FI complexes are not activated by these Al/Mg compositions. The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films; however, their mechanical characteristics do not exceed those obtained using MAO.

Keywords: FI catalysts; copolymerization; ethylene/higher olefin copolymer; polymerization; titanium(IV); ultra-high molecular weight polyethylene; zirconium(IV).

Abstract

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