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    Combs and Bottlebrushes in a Melt
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    † Department of Polymer Science, University of Akron, Akron, Ohio 44325, United States
    ‡ Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3220, United States
    *E-mail [email protected] (A.V.D.).
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    Macromolecules

    Cite this: Macromolecules 2017, 50, 8, 3430–3437
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    https://doi.org/10.1021/acs.macromol.7b00364
    Published April 11, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    We use a combination of the coarse-grained molecular dynamics simulations and scaling analysis to study conformations of bottlebrush and comb-like polymers in a melt. Our analysis shows that a crossover between comb and bottlebrush regimes is controlled by the crowding parameter, Φ, describing overlap between neighboring macromolecules. In comb-like systems characterized by a sparse grafting of side chains (Φ < 1), the side chains and backbones belonging to neighboring macromolecules interpenetrate. However, in bottlebrushes with densely grafted side chains (Φ ≥ 1), the interpenetration between macromolecules is suppressed by steric repulsion between side chains. In this regime, bottlebrush macromolecules can be viewed as filaments with diameter proportional to size of the side chains. For flexible side chains, the crowding parameter is given by Φ ≈ [v/(lb)3/2][(nsc/ng + 1)/nsc1/2], which depends on both the architectural parameters (degree of polymerization of the side chains, nsc, and number of backbone bonds between side chains, ng) and chemical structure of monomers (bond length l, monomer excluded volume v, and Kuhn length, b). Molecular dynamics simulations corroborate this classification of graft polymers and show that the effective macromolecule Kuhn length, bK, and the mean-square end-to-end distance of the backbone, ⟨Re,bb2⟩, are universal functions of the crowding parameter Φ for all studied systems.

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    Cite this: Macromolecules 2017, 50, 8, 3430–3437
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    https://doi.org/10.1021/acs.macromol.7b00364
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