Ethylene polymerization of the new titanium complexes bearing a phosphine oxide‐bridged bisphenolato ligand

A series of novel titanium(IV) complexes combining a phosphine oxide-bridged bisphenolato ligand TiCl2{2,2'-O=P-R-3 (4-R-2-6-R-1-C6H2O)(2)}(THF) (6a: R-1 = tBu, R-2 - H, R-3 Ph; 6b: R-1 - Ph, R-2 = H, R-3 = Ph; 6c: R-1 = R-2 = tBu, R-3 = Ph; 6d: R-1 = R-2 cumyl, R-3 = Ph; 6e: R-1 = tBu, R-2 = H, R-3 = PhF5) were prepared by the reaction of corresponding bisphenolato ligands with TiCl4 in THF. X-ray analysis reveals that complex 6a adopts distorted octahedral geometry around the titanium center. These catalysts were performed for ethylene polymerization in the presence of modified methyaluminoxane (MMAO).

[1]  A. White,et al.  Group 4 Metal Olefin Polymerization Catalysts Stabilized by Bidentate O,P Ligands , 2008 .

[2]  P. Sudhakar.  Titanium and zirconium complexes containing modified TREN ligands for the polymerization of 1-alkenes—A comparative study , 2007 .

[3]  Jiling. Huang,et al.  Synthesis of double silylene‐bridged binuclear zirconium complexes and their use as catalysts for olefin polymerization , 2007 .

[4]  G. Sundararajan,et al.  Polymerization of 1‐olefins by zirconium/titanium precatalysts with O,N,O‐ligating atoms—can aggregation of catalyst be inferred from the reaction profile? , 2007 .

[5]  Wen‐Hua Sun,et al.  Highly active ethylene polymerization and copolymerization with norbornene using bis(imino-indolide) titanium dichloride-MAO system , 2007 .

[6]  J. Seppälä,et al.  Propylene polymerizations with a binary metallocene system—Chain shuttling caused by trimethylaluminium between active catalyst centers , 2007 .

[7]  Zhicheng Zhang,et al.  Copolymerizations of ethylene and polar comonomers with bis(phenoxyketimine) group IV complexes: Effects of the central metal properties , 2007 .

[8]  Y. Oda,et al.  Synthesis and characterization of phosphorous-bridged bisphenoxy titanium complexes and their application to ethylene polymerization , 2006 .

[9]  P. Sudhakar,et al.  New chiral [N,N,N]‐ligand containing titanium/zirconium precatalysts for 1‐hexene polymerization , 2006 .

[10]  K. Müllen,et al.  Ultrahigh molecular weight polyethylene produced by a bis(phenoxy-imine) titanium complex supported on latex particles , 2006 .

[11]  R. Mülhaupt,et al.  Copolymerization of ethylene with styrene catalyzed by a linked bis(phenolato) titanium catalyst , 2006 .

[12]  Z. Goldschmidt,et al.  Polymerization of 4‐methylpentene and vinylcyclohexane by amine bis(phenolate) titanium and zirconium complexes , 2006 .

[13]  David J. Williams,et al.  Combining hard and soft donors in early-transition-metal olefin polymerization catalysts. , 2006, Inorganic chemistry.

[14]  Liming Tang,et al.  Ethylene/α‐olefin copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane , 2005 .

[15]  Li-Ming Tang,et al.  Titanium complexes bearing aromatic-substituted β-enaminoketonato ligands: Syntheses, structure and olefin polymerization behavior , 2005 .

[16]  J. Okuda,et al.  Synthesis of branched polyethylene by ethylene homopolymerization using titanium catalysts that contain a bridged bis(phenolate) ligand , 2004 .

[17]  Yue-sheng Li,et al.  New Titanium Complexes with Two β-Enaminoketonato Chelate Ligands: Syntheses, Structures, and Olefin Polymerization Activities , 2004 .

[18]  Tsukasa Matsuo,et al.  Titanium N-heterocyclic carbene complexes incorporating an imidazolium-linked bis(phenol). , 2003, Chemical communications.

[19]  R. Mülhaupt,et al.  Titanium and zirconium complexes that contain a tridentate bis(phenolato) ligand of the [OOO]-type , 2003 .

[20]  H. Terao,et al.  Fluorine- and trimethylsilyl-containing phenoxy--imine Ti complex for highly syndiotactic living polypropylenes with extremely high melting temperatures. , 2002, Journal of the American Chemical Society.

[21]  T. Nakano,et al.  New Titanium Complexes Having Two Pyrrolide−Imine Chelate Ligands: Syntheses, Structures, and Ethylene Polymerization Behavior , 2001 .

[22]  T. Nakano,et al.  A Family of Zirconium Complexes Having Two Phenoxy−Imine Chelate Ligands for Olefin Polymerization , 2001 .

[23]  G. Coates,et al.  A new catalyst for highly syndiospecific living olefin polymerization: homopolymers and block copolymers from ethylene and propylene. , 2001, Journal of the American Chemical Society.

[24]  H. Geneste,et al.  2-Substituted 4-(Trifluoromethyl)phenols by Directed ortho-Lithiation , 2001 .

[25]  T. Nakano,et al.  Post-Metallocenes: New Bis(pyrrolyl-2-aldiminato) Titanium Complexes for Ethylene Polymerization , 2000 .

[26]  Tian,et al.  Development of a Diversity-Based Approach for the Discovery of Stereoselective Polymerization Catalysts: Identification of a Catalyst for the Synthesis of Syndiotactic Polypropylene This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineer , 2000, Angewandte Chemie.

[27]  Tatsuya Miyatake,et al.  Titanium and vanadium based non‐metallocene catalysts for olefin polymerization , 2000 .

[28]  A. Harada,et al.  Titanium Complexes Having Chelating Diaryloxo Ligands Bridged by Tellurium and Their Catalytic Behavior in the Polymerization of Ethylene , 2000 .

[29]  T. Weyhermüller,et al.  Isolation, structural and spectroscopic investigations of complexes with tridentate [O,P,O] and [O,O,O] donor ligands , 2000 .

[30]  G. Britovsek,et al.  The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes. , 1999, Angewandte Chemie.

[31]  W. Massa,et al.  Synthesis and structural characterization of titanium complexes containing a sulfinyl-bridged bis (phenolato) ligand , 1998 .

[32]  R. Mülhaupt,et al.  NINE-MEMBERED TITANACYCLIC COMPLEXES BASED ON AN ETHYLENE-BRIDGED BIS(PHENOLATO) LIGAND : SYNTHESIS, STRUCTURE, AND OLEFIN POLYMERIZATION ACTIVITY , 1997 .

[33]  N. Mori,et al.  Chemical Ecology of Astigmatid Mites. Part XLVIII. Facile Synthesis of 2-Hydroxy-6-methylbenzaldehyde, an Alarm and Sex Pheromone Component of Astigmatid Mites. , 1997 .

[34]  R. Mülhaupt,et al.  Copolymerization of Ethene with Styrene Using Methylaluminoxane-Activated Bis(phenolate) Complexes , 1997 .

[35]  W. Massa,et al.  Titanium Complexes of Chelating Bis(phenolato) Ligands with Long Titanium−Sulfur Bonds. A Novel Type of Ancillary Ligand for Olefin Polymerization Catalysts† , 1996 .

[36]  S. V. Meille,et al.  Molecular structure of 2,2′-thiobis(4-methyl-6-tert-butylphenoxy) titanium diisopropoxy. Influence of titanium-sulfur interaction on coordination geometry , 1996 .

[37]  A. Orpen,et al.  Polymerization of .alpha.-Olefins and Butadiene and Catalytic Cyclotrimerization of 1-Alkynes by a New Class of Group IV Catalysts. Control of Molecular Weight and Polymer Microstructure via Ligand Tuning in Sterically Hindered Chelating Phenoxide Titanium and Zirconium Species , 1995 .

[38]  M. Kakugo,et al.  Ti complex catalysts including thiobisphenoxy group as a ligand for olefin polymerization , 1993 .

[39]  M. Kakugo,et al.  2,2'-Thiobis (6-tert-butyl-4-methylphenoxy) titanium or zirconium complex-methylalumoxane catalysts for polymerization of olefins , 1989 .

[40]  D. Magnelli,et al.  Synthesis and Characterization of Some Perfluorophenylphosphine Derivatives , 1966 .