Living Polymerization of Propene with a Chelating Diamide Complex of Titanium Using Dried Methylaluminoxane

Hagimoto, Hitoshi; Shiono, Takeshi; Ikeda, Tomiki

doi:10.1002/1521-3927(20020101)23:1<73::aid-marc73>3.0.co;2-q

Cited by 66 publications

(41 citation statements)

References 13 publications

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“…We therefore removed the remaining Me 3 Al and i Bu 3 Al in MMAO by repeated vacuum drying and successive redissolving in heptanes to obtain R 3 Al-free MMAO (dMMAO). 28 Figure 5 shows the 1 H NMR spectra of MMAO and dMMAO in tetrahydrofuran-d 8 . The contents of each Al species were calculated from the relative intensities Table 5.…”

Section: Activation With R 3 Al-free Modified Mao (Mmao)mentioning

confidence: 99%

“…We also succeeded in the living polymerization of propene with the [Ar'N(CH 2 ) 3 NAr']TiMe 2 -dMMAO (Ar'¼2,6-i Pr 2 C 6 H 3 ) system in heptane at 0 1C. 28 As the potential of dMMAO as a cocatalyst in heptane was confirmed, we investigated the effect of solvents, namely toluene, chlorobenzene (CB) and ortho-dichlorobenzene (o-DCB), on propene polymerization with 1-dMMAO by a batch method conducted over 1 h. 30 The polymerizations quantitatively proceeded, irrespective of the amount of propene charged and the solvent employed. The produced polymers showed narrow MWDs of 1.14B1.39.…”

Section: Activation With R 3 Al-free Modified Mao (Mmao)mentioning

confidence: 99%

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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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Section: Activation With R 3 Al-free Modified Mao (Mmao)mentioning

confidence: 99%

Section: Activation With R 3 Al-free Modified Mao (Mmao)mentioning

confidence: 99%

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

Shiono

2011

Polym J

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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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“…MMAO solution in toluene was supplied by TosohFineChem Co. Dried modified methylalminoxane (dMMAO) was prepared by evaporation of the MMAO solution in toluene, followed by repeated redissolving in heptane and evaporation [10].…”

Section: General Remarksmentioning

confidence: 99%

“…Thus, we synthesized a series of titanium complexes with ansa-(fluorenyl)(cyclododecylamido) ligands, Me2Si(η 3 -R)(N-c-C12H23)TiMe2 (R = fluorenyl (5), 2,7-t Bu2fluorenyl (6), 3,6-t Bu2fluorenyl (7)), and examined their catalytic behavior for the copolymerization of E with IB and d-limonene (LM) [5]. In this report, some other titanium complexes (8)(9)(10) bearing different secondary and primary alkyl-amido groups were synthesized and their catalytic behaviors for the E-IB copolymerization were examined (Scheme 1). The effects of cocatalysts on the E-IB copolymerization by 6 were also investigated.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of Ethylene with Isobutylene and Limonene Catalyzed by Titanium Complexes with Various ansa-(Fluorenyl)(alkylamido) Ligand

Nakayama

Sogo

Tanaka

et al. 2013

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Abstract.A series of titanium complexes bearing ansa-(fluorenyl)(amido) ligands with cyclohexylamido, isopropylamido, and isobutylamido groups were synthesized and their catalytic behaviors for the copolymerization of ethylene with isobutylene were compared with those with cyclododecylamido and tert-butylamido groups. The effects of cocatalyst on the ethylene-isobutylene copolymerization by a titanium complex having ansa-(fluorenyl)(cyclododecylamido) ligand were examined. The catalytic activity of the titanium complex for ethylene-limonene copolymerization was also further investigated.

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Living Polymerization of Propene with a Chelating Diamide Complex of Titanium Using Dried Methylaluminoxane

Cited by 66 publications

References 13 publications

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

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

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

Copolymerization of Ethylene with Isobutylene and Limonene Catalyzed by Titanium Complexes with Various ansa-(Fluorenyl)(alkylamido) Ligand

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