Mesoscopic modeling of the polymerization, morphology, and crystallization of stereoblock and stereoregular polypropylenes

Abstract

AbstractThermoplastic elastomers require domains that act as physical crosslinks, and these can be either glassy regions or crystallites. For crystallites in a polymer such as polypropylene (PP), the challenge is to develop polymerizations that form the long stereoregular chain sequences required to produce crystallites large enough to act as stable temporary crosslinks but not so many of them that the material becomes a significantly crystalline thermoplastic rather than an elastomer. For PP, the requirement is for long isotactic sequences within predominantly elastomeric atactic chains, and catalysts required to achieve such an unusual stereoblock structure are now available. This provided encouragement for the simulations described herein that illustrate some relationships between polymerization mechanisms and distributions of isotactic sequences (particularly those long enough to crystallize). A Windle‐type Monte Carlo algorithm was then applied to arrays of the representative PP chains in searches for matches of crystallizable sequences. This approach provided estimates of degrees of crystallinity, melting points, interfacial free energies, standard free energies of fusion, and Young's moduli at small extensions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 840–853, 2002