Highly Efficient Ethylene/Cyclopentene Copolymerization with Exclusive 1,2‐Cyclopentene Incorporation by (Cyclopentadienyl)(ketimide)titanium(IV) Complex–MAO Catalysts

The (cyclopentadienyl)-(ketimide)titanium(IV) complex (t-BuC 5 H 4 )TiCl 2 [N=C(t-Bu) 2 ] exhibited remarkable catalytic activities (1.99-3.16 x 10 4 kg polymer/mol Ti·h) with efficient cyclopentene incorporation in ethylene/cyclopentene copolymerization in the presence of methylaluminoxane (MAO). The polymerization took place with exclusive 1,2-cyclopentene incorporation, affording high molecular weight (alternating) copolymers (cyclopentene <43.6 mol%) with uniform distributions. The effect of the cyclopentadienyl fragment (Cp') in the copolymerization using Cp'TiCl 2 [N=C(t-Bu) 2 ] [Cp'=indenyl, t-BuC 5 H 4 , C 5 Me 5 (Cp*), C 5 H 5 (Cp)] has been explored in the presence of MAO; the Cp' plays an important key role in terms of both activity and efficient cyclopentene incorporation.

[1]  Jingyu Liu,et al.  Effect of ketimide ligand for ethylene polymerization and ethylene/norbornene copolymerization catalyzed by (cyclopentadienyl)(ketimide)titanium complexes–MAO catalyst systems: Structural analysis for Cp∗TiCl2(NCPh2) , 2007 .

[2]  Boonyarach Kitiyanan,et al.  Nonbridged half-metallocenes containing anionic ancillary donor ligands: New promising candidates as catalysts for precise olefin polymerization , 2007 .

[3]  M. Fujiki,et al.  Notable norbornene (NBE) incorporation in ethylene-NBE copolymerization catalysed by nonbridged half-titanocenes: better correlation between NBE incorporation and coordination energy. , 2006, Chemical communications.

[4]  S. Coles,et al.  Salicylaldiminato Pyrrolylaldiminato Group 4 Metal Alkene Polymerization Catalysts: Combining High Activity with High Comonomer Incorporation. , 2006 .

[5]  T. Shiono,et al.  Living Random Copolymerization of Propylene and Norbornene with ansa-Fluorenylamidodimethyltitanium Complex: Synthesis of Novel Syndiotactic Polypropylene-b-poly(propylene-ran-norbornene) , 2006 .

[6]  Li-Ming Tang,et al.  Copolymerization of ethylene and cyclopentene with bis(β-enaminoketonato) titanium complexes† , 2005 .

[7]  Naofumi Naga.  Copolymerization of ethylene with cycloolefins or cyclodiolefins by a constrained-geometry catalyst , 2005 .

[8]  Wei Wang,et al.  Copolymerization of ethylene with cyclohexene (CHE) catalyzed by nonbridged half-titanocenes containing aryloxo ligand: notable effect of both cyclopentadienyl and anionic donor ligand for efficient CHE incorporation. , 2005, Journal of the American Chemical Society.

[9]  Wei Wang,et al.  Effect of Cyclopentadienyl Fragment in Copolymerization of Ethylene with Cyclic Olefins Catalyzed by Non‐Bridged (Aryloxo)(cyclopentadienyl)titanium(IV) Complexes , 2005 .

[10]  T. Ikeda,et al.  Random Copolymerization of Propene and Norbornene with ansa-Fluorenylamidodimethyltitanium-Based Catalysts , 2005 .

[11]  Tariqul Hasan,et al.  Ethene−Norbornene Copolymer with High Norbornene Content Produced by ansa-Fluorenylamidodimethyltitanium Complex Using a Suitable Activator , 2004 .

[12]  M. Fujiki,et al.  Olefin polymerization by (cyclopentadienyl)(ketimide)titanium(IV) complexes of the type, Cp′TiCl2(NCtBu2)-methylaluminoxane (MAO) catalyst systems , 2004 .

[13]  T. Nakano,et al.  Living copolymerization of ethylene with norbornene catalyzed by bis(pyrrolide-imine) titanium complexes with MAO. , 2004, Journal of the American Chemical Society.

[14]  R. Waymouth,et al.  Catalytic syntheses of alternating, stereoregular ethylene/cycloolefin copolymers ☆ , 2004 .

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

[16]  M. Fujiki,et al.  Efficient Ethylene/Norbornene Copolymerization by (Aryloxo)(indenyl)titanium(IV) Complexes−MAO Catalyst System , 2003 .

[17]  R. Waymouth,et al.  Alternating stereospecific copolymerization of cyclopentene and ethylene with constrained geometry catalysts. , 2003, Chemical communications.

[18]  G. Coates,et al.  Synthesis and Characterization of Alternating and Multiblock Copolymers from Ethylene and Cyclopentene , 2002 .

[19]  Naofumi Naga,et al.  Ethylene/Styrene Copolymerization by Various (Cyclopentadienyl)(aryloxy)titanium(IV) Complexes-MAO Catalyst Systems , 2002 .

[20]  T. Nakano,et al.  Living ethylene/norbornene copolymerisation catalyzed by titanium complexes having two pyrrolide-imine chelate ligands. , 2002, Chemical communications.

[21]  R. Mülhaupt,et al.  Poly(ethene-co-norbornene) Obtained with a Constrained Geometry Catalyst. A Study of Reaction Kinetics and Copolymer Properties , 2002 .

[22]  M. C. Sacchi,et al.  Ethylene−Norbornene Copolymers from Metallocene-Based Catalysts: Microstructure at Tetrad Level and Reactivity Ratios , 2002 .

[23]  Naofumi Naga,et al.  Copolymerization of ethylene and cyclopentene with zirconocene catalysts: Effect of ligand structure of zirconocenes , 2002 .

[24]  A. Grassi,et al.  Crystalline alternating sequences identified in ethylene-co-norbornene polymers produced by the (η5-C2B9H11)Zr(NEt2)2(NHEt2)-AliBu3 catalyst , 2001 .

[25]  W. Kaminsky,et al.  Copolymerization of ethene with cyclic and other sterically hindered olefins , 2001 .

[26]  M. C. Sacchi,et al.  Stereoregular and stereoirregular alternating ethylene-norbornene copolymers , 2001 .

[27]  L. Zetta,et al.  Ethylene-norbornene copolymer microstructure. Assessment and advances based on assignments of 13C NMR spectra , 2000 .

[28]  W. Piers,et al.  The Mechanism of Methane Elimination in B(C6F5)3-Initiated Monocyclopentadienyl-Ketimide Titanium and Related Olefin Polymerization Catalysts , 2000 .

[29]  Laura Boggioni,et al.  The Conformational Characteristics of Ethylene−Norbornene Copolymers and Their Influence on the 13C NMR Spectra , 1999 .

[30]  R. Waymouth,et al.  Ethylene/Norbornene Copolymerizations with Titanium CpA Catalysts , 1999 .

[31]  K. Gardner,et al.  Addition Polymerization of Cyclopentene with Nickel and Palladium Catalysts , 1998 .

[32]  Ruchatz,et al.  Ethene-Norbornene Copolymerization Using Homogenous Metallocene and Half-Sandwich Catalysts: Kinetics and Relationships between Catalyst Structure and Polymer Structure. 1. Kinetics of the Ethene-Norbornene Copolymerization Using the , 1998, Macromolecules.

[33]  D. J. Crowther,et al.  Stereoregular, alternating ethylene-norbornene copolymers from monocyclopentadienyl catalysts activated with non-coordinating discrete anions , 1998 .

[34]  A. Jerschow,et al.  Nuclear magnetic resonance evidence for a new microstructure in ethene-cyclopentene copolymers , 1995 .

[35]  H. Cherdron,et al.  Cycloolefin-copolymere: Eine neue klasse transparenter thermoplaste† , 1994 .

[36]  Werner Kaminsky.  Olefinpolymerisation mittels Metallocenkatalysatoren , 1994 .

[37]  W. Kaminsky,et al.  Copolymerization of cycloalkenes with ethylene in presence of chiral zirconocene catalysts , 1989 .