Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers

Jiang, Liuyin; Nykypanchuk, Dmytro; Pastore, Vincent J.; Rzayev, Javid

doi:10.1021/acs.macromol.9b01756

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 »« less

Authors:

Jiang, Liuyin ^[1];

^[2];

^[1];

^[1]

Univ. at Buffalo, The State Univ. of New York, Buffalo, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: 2019-10-22

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.  doi:10.1021/acs.macromol.9b01756.

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                    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

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                    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.

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@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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Cited by: 21 works

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Figures / Tables:

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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