Syndiospecific Living Polymerization of Propene with [t-BuNSiMe2Flu]TiMe2 Using MAO as Cocatalyst

Hasan, Tariqul; Ioku, Atau; Nishii, Kei; Shiono, Takeshi; Ikeda, Tomiki

doi:10.1021/ma0017438

Cited by 140 publications

(112 citation statements)

References 14 publications

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“…In fact, both the catalytic activity and the M n values decreased upon increasing the α-olefin content in the NBE/1-octene copolymerization using [H 2 C(Me 2 C 5 H 2 ) 2 ]ZrCl 2 [58]. As one exception, the fluorenyl-based half-titanocenes, exemplified by [Me 2 Si(fluorenyl)-(N t Bu)]TiMe 2 , (Flu-CGC, 4) reported by Shiono et al afforded copolymers of NBE not only with propylene [60,61], but also with α-olefin (1-hexene, 1-octene, and 1-decene) [62,63], and the resultant copolymers possessed narrow molecular weight distributions because of the nature of livingness, as observed in the NBE [64,65] and the propylene polymerizations [66]. Both the activity (especially) and the α-olefin content were affected by the ligand substituents and cocatalyst employed [60][61][62][63].…”

Section: Copolymerization Of α-Olefin With Norbornene (Nbe) or Tetracmentioning

confidence: 98%

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Zhao

Nomura

2016

Catalysts

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Abstract:Selected results for the synthesis of cyclic olefin copolymers (COCs)-especially copolymerizations of norbornene (NBE) or tetracyclododecene (TCD) with ethylene and α-olefins (1-hexene, 1-octene, 1-dodecene)-using group 4 transition metal (titanium and zirconium) complex catalysts have been reviewed. Half-titanocenes containing an anionic ancillary donor ligand, Cp'TiX 2 (Y) (Cp' = cyclopentadienyl; X = halogen, alkyl; Y = anionic donor ligand such as aryloxo, ketimide, imidazolin-2-iminato, etc.), are effective catalysts for efficient synthesis of new COCs; ligand modifications play an important role for the desired copolymerization. These new COCs possess promising properties (high transparency, thermal resistance (high glass transition temperature), low water absorption, etc.), thus it is demonstrated that the design of an efficient catalyst plays an essential role for the synthesis of new fine polyolefins with specified properties.

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Section: Copolymerization Of α-Olefin With Norbornene (Nbe) or Tetracmentioning

confidence: 98%

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Zhao

Nomura

2016

Catalysts

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“…We therefore prepared Me 3 Al-free MAO by vacuum drying a toluene solution of MAO, followed by washing with hexane and applying it as a cocatalyst. 26 Thereafter, the MAO treated via this procedure was denoted as dMAO, an abbreviation of dried MAO. Figure 3 shows the 1 H NMR spectra of MAO and dMAO, which indicates that dMAO does not contain free Me 3 Al.…”

Section: Polymerization Of Propene and Higher 1-alkenementioning

confidence: 99%

“…26 Hence, the polymerization rate can be monitored by the flow rate of propene introduced. CGC-Ti was also used for comparison.…”

Section: Polymerization Of Propene and Higher 1-alkenementioning

confidence: 99%

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Shiono

2011

Polym J

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This article reviews the living homopolymerization and copolymerization of propene, 1-alkene and norbornene with ansadimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(g 3 -C 13 H 8 )(g 1 -N t Bu)TiMe 2 and its derivatives, correlating the effects of cocatalysts, solvents, polymerization conditions and the substituents of the fluorenyl ligand with catalytic features, such as livingness, initiation efficiency, propagation rate, syndiospecificity and copolymerization ability. The synthesis of novel olefin block copolymers and their catalytic synthesis are also introduced using this living system. Polymer Journal (2011) 43, 331-351; doi:10.1038/pj.2011 Keywords: cycloolefin copolymer; living polymerization; norbornene; propene; single-site catalyst; syndiospecific polymerization; 1-alkene A living polymerization system, in which neither chain transfer nor deactivation occurs, affords polymers with predictable molecular weights and narrow molecular weight distributions (MWDs). Living polymerization techniques are utilized for the synthesis of terminally functionalized polymers and block copolymers. Another feature of living polymerization is its simple kinetics. Because neither chain transfer nor deactivation occurs in living polymerization, the number of polymer chains (N) is equal to the number of active centers ([C*]), and the number-average molecular weight (M n ) directly reflects the propagation rate. In living polymerization, the propagation rate can be evaluated from the M n value and the polymerization time. As chain transfer via b-elimination and/or transmetalation with trialkylaluminum as a cocatalyst is inevitable in conventional Ziegler-Natta catalytic systems; homogeneous V(acac) 3 /Et 2 AlCl (where acac is acetylacetonate or its analog) had previously been the only catalytic system that produced syndiotactic-rich living polypropylene (PP) atThe development of metallocene catalysts has enabled us to produce a variety of uniform olefin copolymers and to control the stereoregularity of poly(1-alkene)s. 3,4 The success of metallocene catalysts has stimulated research on transition metal complexes for olefin polymerization, 5-7 so-called single-site catalysts, which has also resulted in various transition metal complexes for the living polymerization of olefins. 8,9 We have also developed a living polymerization system using ansa-dimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(Z 3 -C 13 H 8 )(Z 1 -N t Bu)TiMe 2 (1), combined with a suitable cocatalyst. The catalytic system allows not only a syndiospecific living polymerization of propene and a 1-alkene but also a living homopolymerization and copolymerization of norbornene with a 1-alkene. We investigated the effect of cocatalyst, solvent and the ligand of the titanium complex on propene polymerization in terms of the livingness of the system. We also synthesized novel olefin block copolymers with the living system. This article reviews the characteristics of 1-based catalysts for tailor-made polyolefins. SYNTHESIS AND STRUCTURES OF TIT...

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“…dMMAO was prepared according to the literature [20,21]. A toluene solution of MMAO was dried under vacuum for 6 h by evaporating solvent, TMA and Al(iBu3) (TIBA).…”

Section: Preparation Of Dried-mmao (Dmmao)mentioning

confidence: 99%

Ethylene/1-Hexene Copolymerization over Different Phases Titania-Supported Zirconocene Catalysts

Wannaborworn¹,

Sriphaisal²,

Praserthdam³

et al. 2015

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Abstract. Ethylene/1-hexene copolymerization was performed over titania-supported zirconocene/dMMAO catalysts. Effects of titania having different phases on the catalytic activity and polymer properties were investigated. It was found that anatase titania exhibited the highest catalytic activity, and afforded copolymer with high 1-hexene incorporation among other titanias. According to TGA result, the stronger interaction between dMMAO and titania for anatase phase led to the highest catalytic activity, because the stronger interaction between cocatalyst and support would prevent the leaching of cocatalyst. Additionally, based on EDX mapping, a good dispersion of dMMAO over support surface is another reason for an increase in the catalytic activity. SEM analysis indicated that no significant change in polymer morphology was found for all supported catalysts. The incorporation of 1-hexene determined by 13 C NMR suggested that titania which possessed high amount of [Al]dMMAO over support surface showed high ability to incorporate 1-hexene. The random copolymers were produced in all systems.

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Syndiospecific Living Polymerization of Propene with [t-BuNSiMe₂Flu]TiMe₂ Using MAO as Cocatalyst

Cited by 140 publications

References 14 publications

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Ethylene/1-Hexene Copolymerization over Different Phases Titania-Supported Zirconocene Catalysts

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