2. Chain Conformation, Crystal Structures, and Structural Disorder in Stereoregular Polymers

  1. Mark M. Green2,
  2. R. J. M. Nolte3 and
  3. E. W. Meijer4
  1. Claudio De Rosa

Published Online: 14 MAY 2004

DOI: 10.1002/0471471895.ch2

Materials-Chirality, Volume 24

Materials-Chirality, Volume 24

How to Cite

De Rosa, C. (2003) Chain Conformation, Crystal Structures, and Structural Disorder in Stereoregular Polymers, 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.ch2

Editor Information

  1. 2

    Polytechnic University, Brooklyn, New York, USA

  2. 3

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

  3. 4

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

Author Information

  1. Dipartimento di Chimica, Università di Napoli “Federico II” Complesso Monte S. Angelo, Via Cintia, 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



  • constitution and configuration of crystalline polymers;
  • conformation of polymer chains in crystalline state – basic principles – helical conformation in isotactic and syndiotactic polymers – conformational energy calculations in isotactic and syndiotactic polymers – helical conformation and optical activity – polydienes – disordered conformations – alternating copolymers;
  • packing of macromolecules in polymer crystals;
  • general principles;
  • symmetry breaking;
  • frustrated polymer crystal structures;
  • disorder in polymer crystals;
  • examples of positional disorder with long-range three-dimensional periodicity maintained only for some characterizing points of structure – disorder in positioning of right- and left-handed helical chains – disorder in positioning of up and down chains – disorder in stacking of ordered layers in macromolecules along one lattice direction – conformational kink-band disorder;
  • solid mesomorphic forms;
  • chiral crystallization of polymers with helical chain conformations


The analysis of the structure of stereoregular crystalline polymers will start with the analysis of the formation of chiral objects (helices) from non-chiral molecules thanks to a stereospecific polymerization and the fact that stereoregular polymers assume, generally, helical conformations. The formation, in some cases, of chiral crystals as a result of the crystallization of isomorphous helical chains will be described. The reasons of the formation of chiral crystal phases by a solid state crystal-crystal transformation are discussed on the basis of a cooperative process. An analysis of the helical conformations assumed by isotactic and syndiotactic polymers will follow; the differences between the helical symmetries in isotactic and syndiotactic chains are discussed on the basis of simple geometrical considerations. The last part of the chapter focuses on the analysis of the crystal packing of stereoregular polymers and on various new phenomena that regulate the local arrangement of polymer chains. In particular, the illustration and the “symmetry breaking” phenomena, found in the packing of polymers, are discussed. Finally, the polymorphic behavior of new stereoregular polymers, related to different helical conformations and/or different mode of packing, are analyzed, and various disorder phenomena, which characterize either the conformation or the arrangement of the chains in the crystallization, are described.