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Influence of Monomer Molecular Structure on the Miscibility of Polymer Blends

  • Karl F. FreedEmail author
  • Jacek Dudowicz
Chapter
Part of the Advances in Polymer Science book series (POLYMER, volume 183)

Abstract

Polymer blends are formulated by mixing polymers with different chemical structures to create new material with beneficial properties of the individual components. While Flory--Huggins (FH) theory explains some basic trends in blend miscibility, the theory completely neglects the dissimilarity in monomer structures that is central to the fabrication of real blends. We systematically investigate the influence of monomer structure on blend miscibility using the lattice cluster theory (LCT) generalization of the FH model in the limit of incompressible, high molecular weight blends where analytical calculations are tractable. The well-known miscibility pattern predicted by FH theory is recovered only for a limited range of monomer size and shape asymmetries, but additional contributions to the LCT entropy and internal energy of mixing for polymers with dissimilarly shaped monomers leads to three additional blend miscibility classes whose behavior is quite different from the prediction of classical FH theory. Several illustrative applications of the LCT provide new molecular-scale interpretations for many nontrivial phenomena occurring in polymer systems. The applications also illustrate the predictive ability of the theory and its usefulness in analyzing thermodynamic data for a wide variety of polymer mixtures, ranging from binary homopolymer blends to various types of copolymer systems.

Polymer blends Miscibility Statistical copolymers Nonrandom mixing effects Monomer structural asymmetry 

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Authors and Affiliations

  1. 1.James Franck Institute and Department of ChemistryThe University of ChicagoChicagoUSA

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