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Ethylene polymerization by phenylenedimethylene-bridged homobinuclear zirconocene/methylaluminoxane systems

โœ Scribed by Junquan Sun; Xijie Liu; Haiying Zhang; Xiaohui Xiao; Feng Lin; Herbert Schumann


Publisher
John Wiley and Sons
Year
2005
Tongue
English
Weight
103 KB
Volume
99
Category
Article
ISSN
0021-8995

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โœฆ Synopsis


Abstract

In the presence of methylaluminoxane (MAO), ethylene polymerization was successfully performed with homobinuclear zirconocene complexes {[(C~5~H~5~)ZrCl~2~](C~5~H~4~CH~2~ C~6~H~4~CH~2~C~5~H~4~)[(C~5~H~5~)ZrCl~2~]; 3o, 4m, and 5p}, which were prepared conveniently by the reaction of disodium(phenylenedimethylene)dicyclopentadienide [C~6~H~4~(CH~2~C~5~H~4~Na)~2~] with 2 equiv of (N^5^โ€Cyclopentadienyl)trichlorozirconium dimethoxyethane (CpZrCl~3~(DME)) in tetrahydrofuran and characterized by ^1^Hโ€NMR and elemental analysis. The effects of the polymerization parameters, such as the temperature, time, concentration of the catalyst, MAO/catalyst molar ratio, and isomeric difference of the homobinuclear metallocene complexes 3o, 4m, and 5p were studied in detail. The results showed that all three catalytic systems had moderate activities in ethylene polymerization and afforded polyethylene with relatively broad polydispersities. The catalytic activity of 4m was somewhat higher than that of 3o and 5p but lower than that of 4,4โ€ฒโ€bis(methylene)biphenyleneโ€bridged zirconocene catalysts; this indicated that the distance between the two metal centers was too short in comparison with a 4,4โ€ฒโ€bis(methylene)biphenylene bridge to increase the catalytic activity. ยฉ 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006


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Ethylene polymerization catalyzed by met
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DFT (density-functional theory) calculations were performed to investigate the thermodynamics of formation of Olefin Separated Ion Pairs (OSIP) Cp2MtCH~/C2H4/Cl2AI[O(A1Me3)AlHMe]; (Cp = q5-C5H5, Mt = Ti, Zr, Me = CH3) from ethylene and Cp2MtMe \* C12AI[O(AlMe3)A1HMe]2, a model of adduct produced by