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Phase Separation and Gelation in Solutions and Blends of Heteroassociative Polymers

  • Scott P. O. Danielsen*
    Scott P. O. Danielsen
    NSF Center for the Chemistry of Molecularly Optimized Networks, Soft Matter Center, and Thomas Lord Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
    *Email: [email protected]
  • Alexander N. Semenov
    Alexander N. Semenov
    Institut Charles Sadron, Centre National de la Recherche Scientifique UPR 22, Université de Strasbourg, 23 rue du Loess, BP 84047, 67034 Strasbourg Cedex 2, France
  • , and 
  • Michael Rubinstein*
    Michael Rubinstein
    NSF Center for the Chemistry of Molecularly Optimized Networks, Soft Matter Center, and Thomas Lord Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
    Departments of Physics, Chemistry, and Biomedical Engineering, Duke University, Durham, North Carolina 27708, United States
    World Primer Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan
    *Email: [email protected]
Cite this: Macromolecules 2023, 56, 14, 5661–5677
Publication Date (Web):July 10, 2023
https://doi.org/10.1021/acs.macromol.3c00854
Copyright © 2023 American Chemical Society

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    Abstract

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    An equilibrium statistical mechanical theory for the formation of reversible networks in two-component solutions of associative polymers is presented to account for the phase behavior due to hydrogen-bonding, metal–ligand, electrostatic, or other pairwise heterotypic associative interactions. We derive explicit analytical expressions for the binding statistics, gelation condition, and free energy, in which we consider polymers of types A and B with many associating groups per chain and consider only A–B association between the groups. The free energy is approximated at the mean-field level, considering overlapping polymer chains with an ideal gas of “stickers” capable of intermolecular association. It is shown that the number of associations is maximized at stoichiometric conditions between A and B associative groups. Accordingly, homogeneous networks are most easily formed near stoichiometric conditions between A and B associative groups, resulting in a re-entrant sol–gel–sol transition as the overall composition is altered. Association and reversible network formation are found to be accompanied by a tendency for phase separation. These results demonstrate that reversibly associating polymers have a large parameter space in terms of molecular design, binding energy, and mixture compositions. Our predictions are expected to be useful in the rational design of interacting polymer mixtures and the formation of reversible networks.

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    Cited By

    This article is cited by 2 publications.

    1. Daniel L. Vigil, Amy Zhang, Kris T. Delaney, Glenn H. Fredrickson. Phase Separation, Reaction Equilibrium, and Self-Assembly in Binary Telechelic Homopolymer Blends. Macromolecules 2023, 56 (24) , 9994-10005. https://doi.org/10.1021/acs.macromol.3c01653
    2. Scott P. O. Danielsen. Chemical Compatibilization, Macro-, and Microphase Separation of Heteroassociative Polymers. Macromolecules 2023, 56 (16) , 6527-6542. https://doi.org/10.1021/acs.macromol.3c00864

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