A Bis(phenoxy-imine)Zr Complex for Ultrahigh-Molecular-Weight Amorphous Ethylene/Propylene Copolymer

Ishii, Seiichi; Saito, Junji; Matsuura, Shuhei; Suzuki, Yasuhiko; Furuyama, Rieko; Mitani, Makoto; Nakano, Takashi; Kashiwa, Norio; Fujita, Terunori

doi:10.1002/1521-3927(20020801)23:12<693::aid-marc693>3.0.co;2-6

Cited by 47 publications

(32 citation statements)

References 2 publications

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“…The above results allow us to postulate the formation of a bis(amine–phenoxy)–Ti complex with Al i Bu 2 attached to the amine donor as a catalytically active species for the 1 /[Ph 3 C] + [B(C 6 F 5 ) 4 ] − /Al i Bu 3 system. Although we observed a similar reduction of bis(phenoxy–imine)–Ti, –Zr, or –Hf complexes with Al i Bu 3 ,22c, 27a, 28a, 46 it is noteworthy that the reduced species is more catalytically active in this case.…”

Section: Resultssupporting

confidence: 50%

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

Suzuki¹,

Tanaka²,

Oshiki³

et al. 2006

Chemistry An Asian Journal

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New Ti and Zr complexes that bear imine-phenoxy chelate ligands, [{2,4-di-tBu-6-(RCH=N)-C6H4O}2MCl2] (1: M = Ti, R = Ph; 2: M = Ti, R = C6F5; 3: M = Zr, R = Ph; 4: M = Zr, R = C6F5), were synthesized and investigated as precatalysts for ethylene polymerization. 1H NMR spectroscopy suggests that these complexes exist as mixtures of structural isomers. X-ray crystallographic analysis of the adduct 1HCl reveals that it exists as a zwitterionic complex in which H and Cl are situated in close proximity to one of the imine nitrogen atoms and the central metal, respectively. The X-ray molecular structure also indicates that one imine phenoxy group with the syn C=N configuration functions as a bidentate ligand, whereas the other, of the anti C=N form, acts as a monodentate phenoxy ligand. Although Zr complexes 3 and 4 with methylaluminoxane (MAO) or [Ph3C]+ [B(C6F5)4]-/AliBu3 displayed moderate activity, the Ti congeners 1 and 2, in association with an appropriate activator, catalyzed ethylene polymerization with high efficiency. Upon activation with MAO at 25 degrees C, 2 displayed a very high activity of 19900 (kg PE) (mol Ti)(-1) h(-1), which is comparable to that for [Cp2TiCl2] and [Cp2ZrCl2], although increasing the polymerization temperature did result in a marked decrease in activity. Complex 2 contains a C6F5 group on the imine nitrogen atom and mediated nonliving-type polymerization, unlike the corresponding salicylaldimine-type complex. Conversely, with [Ph3C]+ [B(C6F5)4]-/AliBu3 activation, 1 exhibited enhanced activity as the temperature was increased (25-75 degrees C) and maintained very high activity for 60 min at 75 degrees C (18740 (kg PE) (mol Ti)(-1) h(-1)). 1H NMR spectroscopic studies of the reaction suggest that this thermally robust catalyst system generates an amine-phenoxy complex as the catalytically active species. The combinations 1/[Ph3C]+ [B(C6F5)4]-/AliBu3 and 2/MAO also worked as high-activity catalysts for the copolymerization of ethylene and propylene.

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Section: Resultssupporting

confidence: 50%

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

Suzuki¹,

Tanaka²,

Oshiki³

et al. 2006

Chemistry An Asian Journal

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“…75 Additionally, Zr-FI catalyst 23 (Fig. 24 The molecular weight probably represents the highest molecular weight known to date for a linear, synthetic copolymer. 24 The molecular weight probably represents the highest molecular weight known to date for a linear, synthetic copolymer.…”

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

confidence: 99%

“…11,12 Such approaches have resulted in the discovery of a number of highly active catalysts, including bis(pyrrolide-imine) group 4 transition metal complexes (PI catalysts), bis(indolide-imine) Ti complexes (II catalysts), bis(phenoxy-ether) Ti complexes (FE catalysts), bis(phenoxy-imine) early transition metal complexes (FI catalysts) and bis(imine-phenoxy) Ti and Zr complexes (IF catalysts) (Fig. The polymers include selective vinyl-and Alterminated PEs, [19][20][21] well-defined and controlled multimodal PEs, 22,23 ultra-high molecular weight ethylene/propylene copolymers, 24 and stereo-and regioirregular high-molecularweight poly(higher a-olefin)s. [25][26][27] In addition, these catalysts can produce highly isotactic and syndiotactic PPs 28-33 and polyolefinic block copolymers from ethylene, propylene, higher a-olefins and norbornene. [13][14][15][16][17][18] Many of these catalysts not only exhibit high ethylene polymerization activities comparable to those obtained with group 4 metallocene catalysts and CGCs, but have also afforded a wide variety of olefin-based polymers with unique architectures.…”

Section: Introductionmentioning

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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“…In general, the catalytic activity increased with the enhancement of , the molecular weight of produced polyethylenes increased considerably, which could not be determined by neither M w using GPC nor viscosity average molecular weight based on [g] due to the rather poor solubility in o-dichlorobenzene or decahydronaphthalene at 135°C. The obtainment of ultra-high molecular weight polyethylenes (UHMWPE) is therefore suggested [50,51].…”

Section: Polymerization Of Ethylene By Complexesmentioning

confidence: 99%

Zirconium complexes with versatile β-diketiminate ligands: Synthesis, structure, and ethylene polymerization

Gong

Huang

2008

Journal of Organometallic Chemistry

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A Bis(phenoxy-imine)Zr Complex for Ultrahigh-Molecular-Weight Amorphous Ethylene/Propylene Copolymer

Cited by 47 publications

References 2 publications

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

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

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

Zirconium complexes with versatile β-diketiminate ligands: Synthesis, structure, and ethylene polymerization

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