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Title: One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile

Morphological control plays a central role in soft materials design. Herein, we report the synthesis of a gradient bottlebrush architecture and its role in directing molecular packing in the solid state. Bottlebrush copolymers with gradient interfaces were prepared via one-shot ring-opening metathesis polymerization of exo- and endo-norbornene-capped macromonomers. Kinetic studies revealed a gradient compositional profile separating the two blocks along the backbone. Side-chain symmetric gradient bottlebrush copolymers exhibited a strong tendency to assemble into cylindrical microstructures, in contrast to their block copolymer analogs with sharp interfaces. Furthermore such exquisite architectural control of the interfacial composition affords a delicate handle to direct macromolecular assembly.
Authors:
 [1] ; ORCiD logo [2] ;  [3] ; 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)
  3. Univ. of Massachusetts, Amherst, MA (United States)
Publication Date:
Report Number(s):
BNL-211265-2019-JAAM
Journal ID: ISSN 2161-1653
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 6; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; bottlebrush copolymers; self-assembly; gradient copolymers; morphology; norbornene reactivity
OSTI Identifier:
1495003

Jiang, Liuyin, Nykypanchuk, Dmytro, Ribbe, Alexander E., and Rzayev, Javid. One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile. United States: N. p., Web. doi:10.1021/acsmacrolett.8b00273.
Jiang, Liuyin, Nykypanchuk, Dmytro, Ribbe, Alexander E., & Rzayev, Javid. One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile. United States. doi:10.1021/acsmacrolett.8b00273.
Jiang, Liuyin, Nykypanchuk, Dmytro, Ribbe, Alexander E., and Rzayev, Javid. 2018. "One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile". United States. doi:10.1021/acsmacrolett.8b00273.
@article{osti_1495003,
title = {One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile},
author = {Jiang, Liuyin and Nykypanchuk, Dmytro and Ribbe, Alexander E. and Rzayev, Javid},
abstractNote = {Morphological control plays a central role in soft materials design. Herein, we report the synthesis of a gradient bottlebrush architecture and its role in directing molecular packing in the solid state. Bottlebrush copolymers with gradient interfaces were prepared via one-shot ring-opening metathesis polymerization of exo- and endo-norbornene-capped macromonomers. Kinetic studies revealed a gradient compositional profile separating the two blocks along the backbone. Side-chain symmetric gradient bottlebrush copolymers exhibited a strong tendency to assemble into cylindrical microstructures, in contrast to their block copolymer analogs with sharp interfaces. Furthermore such exquisite architectural control of the interfacial composition affords a delicate handle to direct macromolecular assembly.},
doi = {10.1021/acsmacrolett.8b00273},
journal = {ACS Macro Letters},
number = 6,
volume = 7,
place = {United States},
year = {2018},
month = {5}
}