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Title: Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers

Abstract

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. As a result, a rich morphological behavior of the gradient bottlebrush copolymers combined withmore » their “user-friendly” one-step synthesis provides a robust and versatile platform for nanostructured material-design and fabrication.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. at Buffalo, The State Univ. of New York, Buffalo, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1579894
Report Number(s):
BNL-212415-2019-JAAM
Journal ID: ISSN 0024-9297
Grant/Contract Number:  
SC0012704; DMR-1709371; DMR-0520547; 654000
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 21; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; bottlebrush copolymers; self-assembly; gradient polymers; morphology; small angle x-ray scattering; nanostructure

Citation Formats

Jiang, Liuyin, Nykypanchuk, Dmytro, Pastore, Vincent J., and Rzayev, Javid. Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.macromol.9b01756.
Jiang, Liuyin, Nykypanchuk, Dmytro, Pastore, Vincent J., & Rzayev, Javid. Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers. United States. https://doi.org/10.1021/acs.macromol.9b01756
Jiang, Liuyin, Nykypanchuk, Dmytro, Pastore, Vincent J., and Rzayev, Javid. Tue . "Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers". United States. https://doi.org/10.1021/acs.macromol.9b01756. https://www.osti.gov/servlets/purl/1579894.
@article{osti_1579894,
title = {Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers},
author = {Jiang, Liuyin and Nykypanchuk, Dmytro and Pastore, Vincent J. and Rzayev, Javid},
abstractNote = {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. As a result, 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.},
doi = {10.1021/acs.macromol.9b01756},
journal = {Macromolecules},
number = 21,
volume = 52,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: One-step synthesis of gradient bottlebrush copolymers by ring-opening metathesis polymerization using exo-norbornene-functionalized PS and endo-norbornene-functionalized PLA macromonomers.

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