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Volumn 33, Issue 25, 2000, Pages 9192-9199

Propene polymerization with catalyst mixtures containing different ansa-zirconocenes: chain transfer to alkylaluminum cocatalysts and formation of stereoblock polymers

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; FRACTIONATION; MIXTURES; MOLECULAR STRUCTURE; POLYMERIZATION; STEREOCHEMISTRY; VOLUME FRACTION; ZIRCONIUM COMPOUNDS;

EID: 0034506819     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma000691j     Document Type: Article
Times cited : (137)

References (47)
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    • note
    • If the MAO used contains an estimated 10% of TMA, about 2 mmol of TMA is present in the reaction mixture. After 30 min, an estimated 0.8 mmol of isopropyl-terminated chains has been produced, such that almost half of the initially present TMA has been consumed and the probability of polymeryl exchange with a Me-Al unit is accordingly diminished.
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    • -] and TMA.
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    • 3 ([Al]:[Zr] 20:1).
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    • Al-mediated polymeryl transfer between the R and S isomers of a racemic zirconocene catalyst is expected to enhance the formation of stereoerrors of the mmrm type compared to a reaction system containing only one of the catalyst enantiomers. Experimental results in this regard are controversial: Reinmuth, A. Dissertation Universität Konstanz, 1992; p 115. Song, W.; Yu, Z.; Chien, J. C. W. J. Organomet. Chem. 1996, 572, 131. Song, W.; Chien, J. C. W. J. Organomet. Chem. 1998, 558, 223. Busico, V.; Brita, D.; Caporaso, L.; Cipullo, R.; Vacatello, M. Macromolecules 1997, 30, 3971. Busico, V.; Cipullo, R. J. Organomet. Chem. 1998, 558, 219.
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    • A small hexane-soluble fraction gave the same atactic pentad distribution as the ether fraction.
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    • The polymer products are slightly sticky powders of homogeneous appearance.
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    • With some effects being probably due also to increasing molar masses, cf. ref 22.
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    • 2-supported rather than homogeneously dissolved metallocene catalysts, which might have different reactivities.
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    • 2 did not show any transfer of the labeled methyl group between these complexes either.
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    • In this respect, methyl-polymeryl exchange between Zr and Al differs from methyl-Cl exchange, which is strongly affected by differences in Zr electron deficiencies: Beck, S.; Brintzinger, H. H. Inorg. Chim. Acta 1998, 270, 376.
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