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Novel titanium(iv) complexes with 2,4-di-tert-butyl-6-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenol in ethene polymerization

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Abstract

Dinuclear (2) and mononuclear dichloride complexes (3) of titanium(iv) isopropoxide with a bidentate phenol alcohol ligand, viz., 2,4-di-tert-butyl-6-(1,1,1,3,3,3-hexafluoro-2-hydroxy-propan-2-yl)phenol, were obtained. The structures of the complexes were confirmed by X-ray diffraction. The dimeric structure of complex 2 is typical of alkoxy compounds and contains the bridging fragment Ti(μ-OPri)2Ti; the coordination polyhedron of the Ti atom is a distorted tetragonal pyramid. In complex 3, the Ti atom has a distorted octahedral environment made up of the O atoms of the ligand, the Cl atoms, and the O atoms of two coordinated propan-2-ol molecules. The catalytic properties of complexes 2 and 3 in ethene polymerization were studied with such promoters as polymethylaluminoxane (MAO), trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, and Et2AlCl-MgBu2. Both the complexes were catalytically active (635 and 540 kg of polyethylene (PE)/(mol of Ti) h atm, respectively) only in the presence of the binary promoter Et2AlCl-MgBu2. The dichloride complexes obtained from a lithium or magnesium salt of the same ligand and TiCl4 without separation from lithium and magnesium chlorides formed as by-products were catalytically active in the presence of MAO, Bui 3Al, and Me3Al. For the catalytic system containing the dichloride complex and MgCl2, the best promoter is Me3Al (1082 kg of PE/(mol of Ti) h atm). The polymer obtained on all the catalytic systems is linear polyethylene characterized by high molecular weight (Mw = = 593900–2000000 g mol−1) and high polydispersity indices (Mw/Mn = 2.8–15). Various conjectures were made about why lithium and magnesium chlorides have the promoting effects.

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Authors and Affiliations

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

    M. V. Solov’ev, S. Ch. Gagieva, V. A. Tuskaev, O. E. Gadalova & B. M. Bulychev

  2. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    N. M. Bravaya

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

    V. N. Khrustalev & A. O. Borissova

Authors
  1. M. V. Solov’ev
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  2. S. Ch. Gagieva
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  3. V. A. Tuskaev
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  4. N. M. Bravaya
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  5. O. E. Gadalova
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  6. V. N. Khrustalev
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  7. A. O. Borissova
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  8. B. M. Bulychev
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Corresponding author

Correspondence to B. M. Bulychev.

Additional information

Dedicated to Academician of the Russian Academy of Sciences O. M. Nefedov on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2185–2194, November, 2011.

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Solov’ev, M.V., Gagieva, S.C., Tuskaev, V.A. et al. Novel titanium(iv) complexes with 2,4-di-tert-butyl-6-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenol in ethene polymerization. Russ Chem Bull 60, 2227–2235 (2011). https://doi.org/10.1007/s11172-011-0342-1

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  • DOI: https://doi.org/10.1007/s11172-011-0342-1

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