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Ethylene homopolymerization and copolymerization with 1-hexene and 1-octene catalyzed by titanium(IV) dichloride TADDOLate complex activated with MAO

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Abstract

The synthesis and olefin polymerization behavior of a new TADDOL-based Ti(IV) complex, (4R,5R)-2,2-dimethyl-α,α,α′,α′-tetrakis[bis-(3,5-trifluoromethyl)phenyl]-1,3-dioxolane-4,5-dimethanolato-titanium(IV) dichloride, are described. Upon activation with MAO, this complex polymerized ethylene, producing ultra-high molecular weight linear polyethylene (UHMWPE) with activities up to 4500 kg mol (Ti)−1 [C2H4]−1 h−1 atm−1 and molecular weights up to 3.25 × 106. The optimal temperature for UHMWPE synthesis was 50 °C. This complex is also capable of copolymerizing ethylene with 1-hexene and 1-octene, giving high molecular weight copolymers with α-olefin incorporation up to 7.8%. The copolymers, obtained with a different ratio of comonomers, are statistical, according to the analysis of the 13C NMR spectra. The reaction parameters that influenced the copolymerization behavior, such as comonomer concentration, reaction temperature and [Al]/[Ti] molar ratio, are examined in detail. Furthermore, high catalytic activities up to 12,531 kg mol(Ti)−1 [C2H4]−1 h−1 atm−1 were observed in copolymerization of ethylene and 1-hexene or 1-octene with the 2/MAO catalytic system. The obtained copolymers possess high molecular weights (Mw = 1.4 × 106—ethylene/1-hexene and 1.86 × 106—ethylene/1-octene) with broad MWD (Mw/Mn = 3.04–8.23) and high comonomer incorporation degrees (up to 6.2 mol% of 1-hexene and 7.8 mol% of 1-octene). Depending on the synthesis conditions, it is possible to form both a statistical copolymer and a block copolymer.

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Acknowledgements

This work was financially supported by the Russian Science Foundation (Project No. 18-13-00375). The synthesis of UHMWPE was financially supported by the Russian Science Foundation (Project No. 16-13-10502). NMR and elemental analysis were performed with the financial support from Ministry of Science and Higher Education of the Russian Federation using the equipment of Center for molecular composition studies of INEOS RAS, Russia.

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, Moscow, Russian Federation, 119992

    Svetlana Ch. Gagieva, Vladislav A. Tuskaev, Olga V. Smirnova, Tamara M. Zvukova, Alexander I. Sizov & Boris M. Bulychev

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, Moscow, Russian Federation, 119991

    Svetlana Ch. Gagieva, Vladislav A. Tuskaev & Anastasiia G. Buyanovskaya

  3. Higher College of Chemistry of Russia, Dimitri Mendeleev University of Chemical Technology of Russia, Moscow, Russian Federation

    Daniele Saracheno

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  1. Svetlana Ch. Gagieva
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Gagieva, S.C., Tuskaev, V.A., Saracheno, D. et al. Ethylene homopolymerization and copolymerization with 1-hexene and 1-octene catalyzed by titanium(IV) dichloride TADDOLate complex activated with MAO. Polym. Bull. 78, 1967–1979 (2021). https://doi.org/10.1007/s00289-020-03195-3

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