Syntheses of multi-stereoblock polybutene-1 using novel monocyclopentadienyltitanium and modified methylaluminoxane catalysts

Zhu, Fangming; Huang, Qigu; Lin, Shangan

doi:10.1002/(sici)1099-0518(19991215)37:24<4497::aid-pola5>3.0.co;2-d

Cited by 13 publications

(15 citation statements)

References 17 publications

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“…Although this can help the process by scavenging oxygen and water from the reaction, it can also cause complications. For example, AlMe 3 can cause variation in catalytic productivity and also changes in the properties of the polymer [115][116][117]. Activation of zirconocene complexes with AlMe 3 can lead to a small amount of activity but are significantly less productive than their MAO-activated analogues [118].…”

Section: Alme 3 and Its Effects On Alkyl Cations And Polymerisationmentioning

confidence: 99%

Group 4 metal complexes for homogeneous olefin polymerisation: a short tutorial review

2015

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The discovery of transition metal-catalysed polymerisation of olefins in the 1950s by Ziegler and Natta was of huge importance. Over the last 30 years, the interest in homogenous polymerisation has not only grown but has changed focus from primarily studying the metallocene complexes of Group 4 to widespread exploration of postmetallocene systems. This is a consequence of extensive patenting of the metallocene catalyst systems, as well as for general interest in the improvement of polyolefin catalysis. The plastics industry produces more than 10 7 tonnes of polyethylene, polypropylene and polystyrene each year worldwide, and the study of well-defined homogenous catalysts is invaluable in uncovering the mechanism of polymerisation and the fundamental properties of the active species. This short Tutorial Review gives an overview of homogenous transition metal Ziegler-Natta catalysis in general as well as an overview of a selection of Group 4 post-metallocene catalysts. An overview of the synthesis and reactions of alkyl cations relevant to olefin polymerisation is also given. Finally, this review summarises recent advances in bimetallic catalysts for olefin polymerisation.

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Section: Alme 3 and Its Effects On Alkyl Cations And Polymerisationmentioning

confidence: 99%

Group 4 metal complexes for homogeneous olefin polymerisation: a short tutorial review

2015

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“…95% 1,2‐insertion). Lin et al14 used a monotitanocene catalyst, Cp*Ti(OBz) 3 /MAO, for the synthesis of multistereoblock polybutene‐1 coupled with a high molecular weight and more one melting point. However, very little work on the preparation of atactic polybutene‐1 with monotitanocene complexes has been reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of high molecular weight atactic polybutene‐1 with a monotitanocene/methylaluminoxane catalyst system

Huang

Wu²,

Zhu³

et al. 2001

J. Polym. Sci. A Polym. Chem.

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A novel catalyst precursor, the monotitanocene (η5‐pentamethylcyclopentadienyl) titanium tricinnamyloxide [Cp*Ti(OCH2CHCHC6H5)3], was synthesized and employed for butene‐1 polymerization in the presence of methylaluminoxane. The effects of the polymerization conditions on the catalytic activity, molecular weight, stereoregularity, and regioregularity of the polymer so obtained were investigated in detail. The results show that the monotitanocene is desirable for the production of atactic polybutene‐1 coupled with good yields under typical polymerization conditions, high molecular weight (weight‐average molecular weight = 5.3–9.6 × 105), and stereoirregularity with the Bernoullian factor B equal to 0.95, which indicates that chain‐end control is predominant. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4068–4073, 2001

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“…[28 -31] In our laboratory, ethylene, [32] propylene, [33,34] and 1-butylene [35,36] homopolymerizations catalyzed by monotitanoFull Paper: Ethylene and butylene-1 were homo-and copolymerized using monotitanocene catalysts composed of g 5 -pentamethylcyclopentadienyl tribenzyloxytitanium [Cp*Ti(OBz) 3 ] and two kinds of solid modified methylaluminoxane (mMAO) containing different amounts of residual trimethylaluminium (TMA). The mMAO1 with lower TMA content to activate Cp*Ti(OBz) 3 for homoand co-polymerization of ethylene and butylene-1 showed higher activity and more butylene-1 incorporation in their copolymers than mMAO2 with higher TMA content.…”

Section: Introductionmentioning

confidence: 99%

“…By varying the amount of comonomer incorporated, it is possible to produce copolymers with densities in the range 0.90-0.94 g/cm 2 .Monotitanocene catalysts have been found to be very effective for syndiospecific polymerization of styrene, [20][21][22][23][24][25] and also for the polymerization of ethylene [26,27] and copolymerization of ethylene with styrene. [28 -31] In our laboratory, ethylene, [32] propylene, [33,34] and 1-butylene [35,36] homopolymerizations catalyzed by monotitano-Full Paper: Ethylene and butylene-1 were homo-and copolymerized using monotitanocene catalysts composed of g 5 -pentamethylcyclopentadienyl tribenzyloxytitanium [Cp*Ti(OBz) 3 ] and two kinds of solid modified methylaluminoxane (mMAO) containing different amounts of residual trimethylaluminium (TMA). The mMAO1 with lower TMA content to activate Cp*Ti(OBz) 3 for homoand co-polymerization of ethylene and butylene-1 showed higher activity and more butylene-1 incorporation in their copolymers than mMAO2 with higher TMA content.…”

mentioning

confidence: 99%

“…[32] Interestingly, it has been found that monotitanocene/MAO catalyzed propylene and butylene-1 homopolymerizations afford atactic polypropylene [33,34] and multi-stereoblock polybutylene-1. [35,36] Commercial ethylene/butylene-1 copolymers contain principally isolated ethyl branches, however, dependent upon the overall butylene-1 incorporation, substantial quantities of 1,3-diethyl branches (dimers), 1,3,5-triethyl branches (trimers), or even larger blocks of ethyl branches may be present. [37] Following up the studies of hompolymerization of ethylene and butylene-1, in this paper we report a monotitanocene catalyst composed of g 5 -pentamethylcyclopentadienyl tribenzyloxy titanium [Cp*Ti(OBz) 3 ] and modified MAO (mMAO) for copolymerization of ethylene with butylene-1 in toluene used as the polymerization medium.…”

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confidence: 99%

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Copolymerization of Ethylene and Butylene-1 with Monotitanocene/Methylaluminoxane as the Catalyst

Zhu¹,

Yang

Huang

et al. 2001

Macromol. Chem. Phys.

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Ethylene and butylene‐1 were homo‐ and co‐ polymerized using monotitanocene catalysts composed of η5‐pentamethylcyclopentadienyl tribenzyloxytitanium [Cp*Ti(OBz)3] and two kinds of solid modified methylaluminoxane (mMAO) containing different amounts of residual trimethylaluminium (TMA). The mMAO1 with lower TMA content to activate Cp*Ti(OBz)3 for homo‐ and co‐ polymerization of ethylene and butylene‐1 showed higher activity and more butylene‐1 incorporation in their copolymers than mMAO2 with higher TMA content. Influences of copolymerization conditions including ethylene/butylene‐1 ratio in the feed, polymerization temperature and Al/Ti molar ratio on activity, butylene‐1 content in copolymers, molecular weight and molecular weight distribution, the triad and tetrad sequence distributions and butylene‐1 content in the copolymers. The monomer reactivity ratios rE and rB (E = ethylene, B = butylene‐1) for ethylene/butylene‐1 copolymerizations were estimated from the 13C NMR spectra. The Cp*Ti(OBz)3/mMAO catalyst gave rise to rErB lower than 1. A correlation between the reactivity ratios and mMAO composition was also made. The thermal properties of copolymers determined by DSC are mainly dependent on the butylene‐1 content in the copolymers.

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Syntheses of multi-stereoblock polybutene-1 using novel monocyclopentadienyltitanium and modified methylaluminoxane catalysts

Cited by 13 publications

References 17 publications

Group 4 metal complexes for homogeneous olefin polymerisation: a short tutorial review

Group 4 metal complexes for homogeneous olefin polymerisation: a short tutorial review

Synthesis and characterization of high molecular weight atactic polybutene‐1 with a monotitanocene/methylaluminoxane catalyst system

Copolymerization of Ethylene and Butylene-1 with Monotitanocene/Methylaluminoxane as the Catalyst

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