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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• 作者：M. V. Solov’ev (1)
  S. Ch. Gagieva (1)
  V. A. Tuskaev (1)
  N. M. Bravaya (2)
  O. E. Gadalova (1)
  V. N. Khrustalev (3)
  A. O. Borissova (3)
  B. M. Bulychev (1) b.bulychev@highp.chem.msu.ru
• 关键词：Key words titanium(iv) – coordination compounds – catalysis – organomagnesium and organoaluminum compounds – promoters – lithium chloride – magnesium chloride – ethene – polymerization
• 刊名：Russian Chemical Bulletin
• 出版年：2011
• 出版时间：November 2011
• 年：2011
• 卷：60
• 期：11
• 页码：2227-2235
• 全文大小：382.8 KB
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• 作者单位：1. Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russian Federation2. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation3. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation
• ISSN：1573-9171

文摘

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 (M_w = = 593900–2000000 g mol?1) and high polydispersity indices (M_w/M_n = 2.8–15). Various conjectures were made about why lithium and magnesium chlorides have the promoting effects.