Titanium Catalysts with Ancillary Phenoxyketimine Ligands for Living Ethylene Polymerization

Reinartz, Stefan; Mason, Andrew F.; Lobkovsky, and Emil B.; Coates, Geoffrey W.

doi:10.1021/om020931e

Cited by 112 publications

(70 citation statements)

References 26 publications

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“…So they possess five possible isomeric structures, (A)-(E) (see Scheme 2 of Supplementary material). Of these, the structure (A) was found to be the most preferred in all Ti or Zr complexes bearing two salicylaldiminato-type ligands [9,15], which coincide with DFT calculations entirely.In b-ketoiminate chelate titanium complexes, the carbon chains of ligands are more flexible than that of salicylaldiminato ligands, 1387-7003/$ -see front matter Ó …”

supporting

confidence: 75%

“…The Group 4 non-metallocene complexes with bidentate anionic [N, O] chelate ligands, which was first reported in 1995 [4], have been of the focus of attention and a variety of [N, O] chelate complexes have been reported for olefin polymerization [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Now the most noticeable catalysts bearing [N, O] chelate ligands are the Group 4 bis(phenoxyimine) ligated complexes reported firstly by Floriani and coworkers in 1995 [5].…”

Section: Introductionmentioning

confidence: 99%

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Titanium complexes with β-ketoiminate chelate ligands for ethylene polymerization: The significant influence of substituents on structures and catalytic activities

Xie

Qian

2009

Inorganic Chemistry Communications

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supporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

Titanium complexes with β-ketoiminate chelate ligands for ethylene polymerization: The significant influence of substituents on structures and catalytic activities

Xie

Qian

2009

Inorganic Chemistry Communications

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“…8g,10b In addition, Ti-FI catalysts 3 and 4 with MAO were also reported by Reinartz, Coates, Suzuki and Fujita to produce nearly monodisperse PEs under limited conditions. 14,15 With these Ti-FI catalysts, however, synthesizing high molecular weight and narrow molecular weight distribution PEs is normally difficult (e.g., 5 min polymerization, atmospheric pressure, 50 C; 1, M n 132000, M w =M n 1.83, 2, M n 24000, M w =M n 1.46).…”

Section: Discovery Of Fluorinated Ti-fi Catalysts For Living Olefin Pmentioning

confidence: 99%

Living Olefin Polymerization and Block Copolymer Formation with FI Catalysts

Sakuma

Weiser

Fujita

2007

Polym J

104

126

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ABSTRACT:This contribution reports on the recent advances in living olefin polymerization catalysis and block copolymer formation made by fluorinated bis(phenoxy-imine)Ti complexes (fluorinated Ti-FI catalysts), which were discovered by Mitsui Chemicals. Fluorinated Ti-FI catalysts are capable of mediating thermally robust living ethylene and highly stereoselective living propylene polymerization. This highly controlled living nature has made it possible to synthesize a wide variety of monodisperse polymers, functionalized polymers and block copolymers from ethylene, propylene, higher -olefins, cyclic olefins and styrene. The living FI polymers possess unique and often previously inaccessible microstructures, and some of the FI polymers were revealed to display unique morphologies and useful material properties. Therefore, the discovery and development of the fluorinated Ti-FI catalysts has not only made a significant impact on living olefin polymerization catalysis but has also given industry opportunities to make unique polyolefin-based materials for the benefit of the world at large. Producing polymers with perfectly controlled molecular weight, molecular weight distribution, composition and architecture has been an ultimate goal in the field of polymer synthesis. Living olefin polymerization permits consecutive enchainment of monomer units without termination, and thus is an excellent way of synthesizing polyolefin-based block copolymers and chain-end functionalized polyolefins as well as precisely controlling molecular weight and composition.1 These living polymers have the potential to be excellent compatibilizers, modifiers, additives and elastomers.Since Doi's pioneering work on living propylene polymerization using a vanadium-based catalyst, 2 much effort has been devoted to the discovery and development of catalysts capable of mediating the living polymerization of olefinic monomers. Recent progress in the rational design of transition metal complexes for olefin polymerization 3 has spurred the development of high performance catalysts based on both early and late transition metal complexes for living olefin polymerization.4 Recent reviews cover much of this work. 5Researchers at Mitsui Chemicals developed phenoxy-imine ligated early transition metal complexes for the controlled (co)polymerization of olefinic monomers (now known as FI catalysts), 6,7 capable of producing a wide variety of unique polymers including selective vinyl-and Al-terminated polyethylenes (PEs), well-defined multimodal PEs, highly isotactic and syndiotactic polypropylenes (iPPs and sPPs), and regio-and stereoirregular high molecular weight poly(higher -olefin)s. 8 After extensive research on FI catalysts, Mitsui researchers in 1999 discovered fluorinated Ti-FI catalysts that can promote unprecedented living ethylene and propylene polymerizations, resulting in the formation of functionalized polymers and block copolymers from ethylene, propylene and higher -olefins. 7,9-11The above results have stimulated even further research on ...

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“…. (6); C(1)-C(6), 1.382(7); C(6)-C(7), 1.442 (7); C(7)-N(1), 1.308 (6); N(1)-C(8), 1.438(7); C(8)-C(13), 1.388(7); C(13)-S(1), 1.778 (6) [13]…”

Section: Synthesis and Characterization Of Ti Complexesunclassified

Ethylene‐Norbornene Copolymerization by New Titanium Complexes Bearing Tridentate Ligands. Sidearm Effects on Catalytic Activity

Gao

Wang

Sun

et al. 2007

Macromol. Rapid Commun.

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Titanium Catalysts with Ancillary Phenoxyketimine Ligands for Living Ethylene Polymerization

Abstract: New titanium catalysts with ancillary, non-fluorinated phenoxyketimine ligands have been synthesized and found to be active for living ethylene polymerization.

Cited by 112 publications

References 26 publications

Titanium complexes with β-ketoiminate chelate ligands for ethylene polymerization: The significant influence of substituents on structures and catalytic activities

Titanium complexes with β-ketoiminate chelate ligands for ethylene polymerization: The significant influence of substituents on structures and catalytic activities

Living Olefin Polymerization and Block Copolymer Formation with FI Catalysts

Ethylene‐Norbornene Copolymerization by New Titanium Complexes Bearing Tridentate Ligands. Sidearm Effects on Catalytic Activity

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