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    Article

    Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers
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    • Liuyin Jiang
      Liuyin Jiang
      Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United States
      More by Liuyin Jiang
    • Dmytro Nykypanchuk
      Dmytro Nykypanchuk
      Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States
      More by Dmytro Nykypanchuk
    • Vincent J. Pastore
      Vincent J. Pastore
      Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United States
      More by Vincent J. Pastore
      Orcidhttp://orcid.org/0000-0002-0666-5885
    • Javid Rzayev*
      Javid Rzayev
      Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United States
      *E-mail: [email protected]
      More by Javid Rzayev
      Orcidhttp://orcid.org/0000-0002-9280-1811
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    Macromolecules

    Cite this: Macromolecules 2019, 52, 21, 8217–8226
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    https://doi.org/10.1021/acs.macromol.9b01756
    Published October 22, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Morphological behavior of PS–PLA bottlebrush copolymers with a compositional gradient along the backbone was investigated by small-angle X-ray scattering (SAXS) analysis and compared to that of their block copolymer analogs. Side chain-symmetric gradient copolymers with varying volume fractions were prepared by one-step ring-opening metathesis polymerization of the corresponding exo- and endo-norbornene-functionalized macromonomers of similar lengths. The morphological map constructed using the SAXS data revealed a wide cylindrical morphology window, including for symmetric compositions, well-ordered lamella morphologies at very low PS volume fractions, and the formation of a rare bicontinuous gyroid morphology. In addition to the highly asymmetric nature of the morphology diagram, the domain spacings obtained for gradient bottlebrush copolymers were significantly smaller (by 30–40%) than the corresponding bottlebrush block copolymer analogs, which was attributed to a nonperpendicular orientation of the gradient bottlebrush backbone at the domain interface. Side chain-asymmetric gradient bottlebrush copolymers were synthesized from PS and PLA macromonomers of different lengths and were demonstrated to assemble into well-ordered cylindrical and lamella morphologies. The results of these studies demonstrate that the gradient interface plays an important role in determining molecular packing during bottlebrush copolymer self-assembly. A rich morphological behavior of the gradient bottlebrush copolymers combined with their “user-friendly” one-step synthesis provides a robust and versatile platform for nanostructured material-design and fabrication.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.9b01756.

    • NMR characterization of macromonomers, SEC and SAXS characterization of bottlebrush copolymers (PDF)

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    Cited By

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    This article is cited by 31 publications.

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    Macromolecules

    Cite this: Macromolecules 2019, 52, 21, 8217–8226
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.9b01756
    Published October 22, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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