1. Chirality of Catalysts for Stereospecific Polymerizations

  1. Mark M. Green3,
  2. R. J. M. Nolte4 and
  3. E. W. Meijer5
  1. Gaetano Guerra1,
  2. Luigi Cavallo1 and
  3. Paolo Corradini2

Published Online: 14 MAY 2004

DOI: 10.1002/0471471895.ch1

Materials-Chirality, Volume 24

Materials-Chirality, Volume 24

How to Cite

Guerra, G., Cavallo, L. and Corradini, P. (2003) Chirality of Catalysts for Stereospecific Polymerizations, in Materials-Chirality, Volume 24 (eds M. M. Green, R. J. M. Nolte and E. W. Meijer), John Wiley & Sons, Inc., Hoboken, NJ, USA. doi: 10.1002/0471471895.ch1

Editor Information

  1. 3

    Polytechnic University, Brooklyn, New York, USA

  2. 4

    Laboratory of Organic Chemistry, Department of Organic Chemistry, NSRIM, University of Nijmegen, Toernooiveld 1, 6525 ED, Nijmegen, The Netherlands

  3. 5

    Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands

Author Information

  1. 1

    Dipartimento di Chimica, Università di Salerno, Via Salvador Allende, I-84081 Salerno, Italy

  2. 2

    Dipartimento di Chimica, Università di Napoli Federico II, Complesso Monte S. Angelo, Via Cintia, I-80126 Napoli, Italy

Publication History

  1. Published Online: 14 MAY 2004
  2. Published Print: 25 SEP 2003

Book Series:

  1. Topics in Stereochemistry

Book Series Editors:

  1. Scott E. Denmark and
  2. Jay Siegel

ISBN Information

Print ISBN: 9780471054979

Online ISBN: 9780471471899

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Keywords:

  • polymerization mechanisms and elements of chirality;
  • chirality in site-controlled stereospecific polymerizations;
  • homogeneous polymerization catalysts: metallocenes – stereoselectivity: mechanism of chiral orientation of growing chain – stereospecifity – stereoselectivities of regioirregular insertions – implications of relative stereoselectivities for primary and secondary insertions;
  • heterogeneous polymerization catalysts – traditional catalytic systems based on TiCl3 – catalytic systems supported on MgCl2;
  • comparison between models for heterogeneous and homogeneous stereospefic catalysts;
  • chirality in chain-end controlled stereospecific polymerization;
  • olefin polymerization – chain-end stereocontrol for primary 1-alkene insertions – chain-end stereocontrol for secondary 1-alkene insertions;
  • styrene and substituted styrene - syndiotactic polymerization;
  • conjugated diene polymerizations

Summary

This chapter deals with the generalities on Ziegler–Natta catalysts. Next to the definitions of regular and stereoregular polymers, the discovery of the processes for polymerization of ethylene and stereospecific polymerization are given. Important for that discovery is the supported catalysts and homogeneous stereospecific catalysts. In the polymerization mechanisms there are many elements of chirality: chirality in site-controlled stereospecific polymerizations; the homogeneous polymerization catalysts; metallocenes; enantioselectivity and stereoselectivity in the propagation; implications of opposite enantioselectivities for primary and secondary insertions; dependence of regioselectivity on stereospecificity; E-Z selectivity for 2-butene copolymerizations; propene-styrene copolymerization; heterogeneous polymerization catalysts (traditionally based on TiCl3—supported on MgCl2); a comparison between Ziegler–Natta and metallocene catalysts; chirality in chain-end controlled stereospecific polymerizations; olefin polymerization; styrene and substituted styrene syndiotactic polymerization; and conjugated dienes polymerizations.