Supporting Effects of Methylaluminoxane on the Living Polymerization of Propylene with a Chelating (Diamide)dimethyltitanium Complex

Hagimoto, Hitoshi; Shiono, Takeshi; Ikeda, Tomiki

doi:10.1002/macp.200350079

Cited by 38 publications

(18 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…29 Propene polymerization by a batch method was then conducted with 1 activated by dMAO or dMMAO in heptane (Table 7). 30 The dMAO system produced the polymer at a 65% conversion with a broad MWD (M w /M n ¼2.10) for 1-h polymerization, whereas the dMMAO system quantitatively produced the polymer with a narrow MWD (M w /M n ¼1.32).…”

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

Self Cite

View full text Add to dashboard Cite

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...

show abstract

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

Self Cite

View full text Add to dashboard Cite

show abstract

“…The anatase phase possessed the lowest BE. According to the literatures [7], the BE for Al2p presented in dMMAO was around 74.9 eV. As we known, the BE refers to the energy levels of atomic core electrons.…”

Section: Characteristics Of Catalyst Supportmentioning

confidence: 91%

“…They offer high catalytic activity and make LLDPE with narrow molecular-weight and chemical composition distribution, thus LLDPE produced from metallocene catalysts show considerably improved mechanical strength and physical properties compared to the conventional Ziegler-Natta [3][4][5][6]. However, the metallocene catalysts have some disadvantages such as lack of morphology control of polymer particle and reactor fouling when they used in homogeneous system [7,8]. This leads to they are still not suitable to apply in an industrial-scale production.…”

Section: Introductionmentioning

confidence: 99%

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

Wannaborworn¹,

Sriphaisal²,

Praserthdam³

et al. 2015

View full text Add to dashboard Cite

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.

show abstract

“…These catalysts are very stable kinetically at 0 0 C and the Mn value of the produced polymers increases with time in a linear manner for over 30 minutes resulting in the formation of atactic polymers of a very high molecular weight, with Mn ~1.5×10 6 . The kp value for the homogeneous catalyst system is ~5 M -1 .s -1 at 0 0 C and when MMAO is supported on silica (this step increases the acidity of Al atoms in MMAO), the kp value increases to ~20 M -1 .s -1 [72,73].…”

Section: Living Polymerization With Fi Catalystmentioning

confidence: 99%

FI Catalyst for Polymerization of Olefin

Damavandi¹,

Ahmadjo²,

Sandaroos³

et al. 2012

Polymerization

View full text Add to dashboard Cite

Supporting Effects of Methylaluminoxane on the Living Polymerization of Propylene with a Chelating (Diamide)dimethyltitanium Complex

Cited by 38 publications

References 10 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

FI Catalyst for Polymerization of Olefin

Contact Info

Product

Resources

About