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[3a] a) Late Transition-Metal Polymerization Catalysis: K. A. Ostoja Starzewski in Nickel Polymerization Catalysts with Ylide Steering Ligands (Eds.: B. Rieger, L. Baugh, S. Kacker, S. Striegler), Wiley-VCH, Weinheim, 2003, pp. 1-26;
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0346182137
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Eds.: B. Rieger, L. Baugh, S. Kacker, S. Striegler, Wiley-VCH, Weinheim
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for other nickel polymerization catalysts, see, for example: c) J. Kukral, A. Abele, G. Müller, B. Rieger in Late Transition Metal Polymerization Catalysis (Eds.: B. Rieger, L. Baugh, S. Kacker, S. Striegler), Wiley-VCH, Weinheim, 2003, pp. 27-58;
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note
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i) In a simple heuristic view, a zirconocene is alkylated and ionized by MAO. The catalytic cycle starts with a zirconocenium cation as the active 14-electron species, with a Zr-Me group as the starting point of the growing chain. The electron-deficient species coordinates ethylene to form a π complex (16-electron species), which rearranges to form a four-membered metallacyclic transition state. This transition state opens the way to a migratory insertion, thereby regenerating an active metallocenium cation now with a Zr-Pr group as the grown chain. The multifold repetition of this sequence of elementary steps leads to the PE macromolecule; j) Important alternative reactions stop the chain growth, while the activity of the catalyst is retained: 1) β-H transfer to the active metal center (also called β-H elimination), 2) β-H transfer to the monomer, and 3) chain transfer to aluminum (i.e. to the co-catalyst). The activity-retaining reaction paths 1-3 (above), which hinder the increased molecular weight of the products, lead to terminated chains with vinyl end-groups and either a) active Zr-H moieties (by β-H transfer to the metal), b) active Zr-Et moieties (by β-H transfer to the monomer), or c) the active Zr-Me species and PE macromolecules attached to Al (by chain transfer to MAO and simultaneous methyl transfer from MAO to Zr). There are other side reactions that deactivate the catalyst.
-
-
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30
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0012338201
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For a review on living olefin polymerizations, see: a) G. W. Coates, P. D. Hustad, S. Reinartz, Angew. Chem. 2002, 114, 2340;
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84986817175
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a divalent samarocene also was reported to produce UHMW-PE at room temperature with very low activity; see: e) H. Yasuda, E. Ihara, M. Morimoto, M. Nodono, S. Yoshioka, M. Furo, Macromol. Symp. 1995, 95, 203;
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0000061624
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non-metallocene bis(phenoxyimine)zirconium catalysts also have been used to prepare UHMW-PE at 25°C; see: f) H. Makio, N. Kashiwa, T. Fujita, Adv. Synth. Catal. 2002, 344, 477.
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