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Metallocene Polymerization: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Polymer Science
Contributor: Helena Kang

In advanced polymer synthesis, metallocene polymerization is a coordination polymerization in which an olefin is enchained at a well-defined sandwich complex of an early transition metal, typically a Group 4 metallocene or ansa-metallocene, after activation to a cationic metal–alkyl species. The concept is bounded by the combination of a bent-metallocene or constrained-geometry precursor, a weakly coordinating counteranion generated by a cocatalyst, and a migratory-insertion mechanism that places each monomer into a metal–carbon bond. Essential features include a single-site active center whose ligand geometry dictates stereochemical control, and an ion-pair environment in which the anion remains associated with the cationic metal without occupying a coordination site required for monomer binding [1][2]. The process is distinguished from classical multi-site Ziegler–Natta polymerization by the molecularly defined ligand sphere and the resulting uniformity of active sites, and from late-metal olefin polymerization by the metallocene architecture and the typical use of methylaluminoxane or related borate activators [3]. Conceptual limits exclude polymerizations in which the metal is not bound to cyclopentadienyl-type ligands and in which chain growth does not proceed by coordination–insertion.

  • metallocene catalyst
  • coordination polymerization
  • ion pair
  • olefin insertion

Advanced Polymer Synthesis and Characterization • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Jiamin Zhou; Simon J. Lancaster; Dennis A. Walker; Stefan Beck; Mark Thornton-Pett; Manfred Bochmann; Synthesis, Structures, and Reactivity of Weakly Coordinating Anions with Delocalized Borate Structure: The Assessment of Anion Effects in Metallocene Polymerization Catalysts. J. Am. Chem. Soc. 2000, 123, 223-237, 10.1021/ja002820h.
  2. Nicholas G. Stahl; Cristiano Zuccaccia; Tryg R. Jensen; Tobin J. Marks; Metallocene Polymerization Catalyst Ion-Pair Aggregation by Cryoscopy and Pulsed Field Gradient Spin−Echo NMR Diffusion Measurements. J. Am. Chem. Soc. 2003, 125, 5256-5257, 10.1021/ja0346375.
  3. Jan Paradies; Gerald Kehr; Roland Fröhlich; Gerhard Erker; Ansa-metallocene polymerization catalysts derived from [2+2]cycloaddition reactions of bis(1-methylethenyl-cyclopentadienyl)zirconium systems. Proc. Natl. Acad. Sci. 2006, 103, 15333-15337, 10.1073/pnas.0602627103.
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