Titanium and Zirconium Complexes with Non‐Salicylaldimine‐Type Imine–Phenoxy Chelate Ligands: Syntheses, Structures, and Ethylene‐Polymerization Behavior

Suzuki, Yasuhiko; Tanaka, Hidetsugu; Oshiki, Toshiyuki; Takai, Kazuhiko; Fujita, Terunori

doi:10.1002/asia.200600256

Cited by 34 publications

(29 citation statements)

References 117 publications

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“…It should be pointed out that Suzuki and Fujita have reported on a structurally related bis(imine-phenoxy)-Ti complex 28 having a C 6 F 5 on the imine-N with MAO activation, which does not promote living ethyl- 40 Interestingly, DFT calculations have indicated that there is virtually no interaction between the ortho-F and the -H (ortho-F/-H distance 3.66 Å ).…”

Section: Mechanistic Features Of Living Polymerization With Fluorinatmentioning

confidence: 99%

Living Olefin Polymerization and Block Copolymer Formation with FI Catalysts

Sakuma

Weiser

Fujita

2007

Polym J

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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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Section: Mechanistic Features Of Living Polymerization With Fluorinatmentioning

confidence: 99%

Living Olefin Polymerization and Block Copolymer Formation with FI Catalysts

Sakuma

Weiser

Fujita

2007

Polym J

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104

126

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“…59,67,68 A Ti-FI catalyst in combination with i-Bu 3 Al/ Ph 3 CB(C 6 F 5 ) 4 , which forms a phenoxy-amine Ti complex as a catalytically active species, displays unique behavior for the polymerization of higher a-olefins. Similar reductions are observed for PI and IF catalysts.…”

Section: Stereo-and Regioirregular High-molecular-weight Poly(higher mentioning

confidence: 99%

“…Unique block copolymers created by fluorinated Ti-FI catalysts a Determined by GPC. Interestingly, DFT calculation studies have demonstrated that there is virtually no interaction between the ortho-F and a b-H on the growing polymer chain (ortho-F/b-H distance 3.66 Å ) for 31/MAO catalyst system 68. c Overall propylene (P) or 1-hexene (H) content (mol%): determined by 1 H NMR.…”

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confidence: 99%

High-performance olefin polymerization catalysts discovered on the basis of a new catalyst design concept

2008

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This critical review highlights the "ligand oriented catalyst design concept", a new catalyst design concept for olefin polymerization that has led to the development of high-activity catalysts. The concept has created a series of highly active ethylene polymerization catalysts, many of which show high activities comparable to those of group 4 metallocene catalysts. Moreover, these catalysts display unique polymerization catalysis to produce a wide variety of polymers that possess unprecedented molecular architectures that are either difficult or impossible to achieve using conventional catalysts (98 references).

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“…Since the ligand structure has a central role in determining the activity as well as the stereospecifity of these types of catalysts, and as shown in Figure 2, flexible electronic nature of a ligand is a key requirement for achieving high activity, the research based on the ligand oriented catalyst design concept has resulted in the discovery of a number of highly active catalysts for the polymerization of ethylene, which include: phenoxy-imine ligand early transition metal complexes (FI catalysts), pyrrolide-imine ligand group 4 transition metal complexes (PI catalysts), indolide-imine ligand Ti complexes (II catalysts), phenoxy-imine ligand group 4 transition metal complexes (IF catalysts), phenoxy-ether ligand Ti complexes (FE catalysts), imine-pyridine ligand late transition metal complexes (IP catalysts), and tris(pyrazolyl) borate ligand Ta complexes (PB catalysts) (Figure 3) [20,[26][27][28][29][30]. In particular, bis(phenoxy-imine) group 4 metal catalysts, developed by Fujita [19][20][21] caused a new revolution in the field of catalytic olefin polymerization.…”

Section: Introductionmentioning

confidence: 99%