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Morphological Behavior of Compositionally Gradient Polystyrene–Polylactide Bottlebrush Copolymers

Journal Article · · Macromolecules
 [1];  [2];  [1];  [1]
  1. Univ. at Buffalo, The State Univ. of New York, Buffalo, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
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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. 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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Grant/Contract Number:
SC0012704
OSTI ID:
1579894
Report Number(s):
BNL--212415-2019-JAAM
Journal Information:
Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 52; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

Figures / Tables (11)

Figure 1(p. 8)figure Figure 1
Figure 2(p. 13)figure Figure 2
Table 1(p. 14)table Table 1
Figure 3(p. 16)figure Figure 3
Figure 4(p. 18)figure Figure 4
Figure 5(p. 18)figure Figure 5
Figure 6(p. 21)figure Figure 6
Figure 7(p. 24)figure Figure 7
Figure 8(p. 26)figure Figure 8
Table 2(p. 26)table Table 2
Figure 9(p. 28)figure Figure 9

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Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
bottlebrush copolymers
gradient polymers
morphology
nanostructure
self-assembly
small angle x-ray scattering