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Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers

  • 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
  • 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
  • , and 
  • 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
Cite this: Macromolecules 2019, 52, 21, 8217–8226
Publication Date (Web):October 22, 2019
https://doi.org/10.1021/acs.macromol.9b01756
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.

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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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