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Title: Synthesis and Self-Assembly of AB n Miktoarm Star Polymers

Abstract

The stability of tetrahedrally close-packed (TCP) phases in block copolymer melts is predicted by theory to depend on molecular architecture, yet no experimental studies to date have probed its effect. Motivated by this open question, here we report an efficient synthesis of asymmetric ABn miktoarm star polymers using functionalized sugars as cores for orthogonal grafting-from block copolymerizations. A combination of ring-opening and atom transfer radical polymerization produced model low dispersity materials comprising a single A = poly(lactide) (L) and multiple B = poly(dodecyl acrylate) (D) arms that amplify “conformational asymmetry” through two concerted effects: the mikto architecture and disparate block statistical segment lengths. Analyzing the self-assembly of LD2 and LD3 samples resulted in the discovery of two TCP phases, σ and A15, that remained stable to significantly higher A-block volume fractions as the number of B arms increased. Finally, these results experimentally establish the importance of conformational asymmetry and molecular architecture as powerful design tools for the self-assembly of block copolymers into non-classical phases.

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [2];  [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of California, Santa Barbara, CA (United States); Univ. of Queensland, Brisbane (Australia)
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1605358
Grant/Contract Number:  
SC0019001; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 3; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; star polymers; self organization; phase transitions; materials; copolymers

Citation Formats

Bates, Morgan W., Barbon, Stephanie M., Levi, Adam E., Lewis, Ronald M., Beech, Haley K., Vonk, Kasper M., Zhang, Cheng, Fredrickson, Glenn H., Hawker, Craig J., and Bates, Christopher M.. Synthesis and Self-Assembly of AB n Miktoarm Star Polymers. United States: N. p., 2020. Web. https://doi.org/10.1021/acsmacrolett.0c00061.
Bates, Morgan W., Barbon, Stephanie M., Levi, Adam E., Lewis, Ronald M., Beech, Haley K., Vonk, Kasper M., Zhang, Cheng, Fredrickson, Glenn H., Hawker, Craig J., & Bates, Christopher M.. Synthesis and Self-Assembly of AB n Miktoarm Star Polymers. United States. https://doi.org/10.1021/acsmacrolett.0c00061
Bates, Morgan W., Barbon, Stephanie M., Levi, Adam E., Lewis, Ronald M., Beech, Haley K., Vonk, Kasper M., Zhang, Cheng, Fredrickson, Glenn H., Hawker, Craig J., and Bates, Christopher M.. Thu . "Synthesis and Self-Assembly of AB n Miktoarm Star Polymers". United States. https://doi.org/10.1021/acsmacrolett.0c00061. https://www.osti.gov/servlets/purl/1605358.
@article{osti_1605358,
title = {Synthesis and Self-Assembly of AB n Miktoarm Star Polymers},
author = {Bates, Morgan W. and Barbon, Stephanie M. and Levi, Adam E. and Lewis, Ronald M. and Beech, Haley K. and Vonk, Kasper M. and Zhang, Cheng and Fredrickson, Glenn H. and Hawker, Craig J. and Bates, Christopher M.},
abstractNote = {The stability of tetrahedrally close-packed (TCP) phases in block copolymer melts is predicted by theory to depend on molecular architecture, yet no experimental studies to date have probed its effect. Motivated by this open question, here we report an efficient synthesis of asymmetric ABn miktoarm star polymers using functionalized sugars as cores for orthogonal grafting-from block copolymerizations. A combination of ring-opening and atom transfer radical polymerization produced model low dispersity materials comprising a single A = poly(lactide) (L) and multiple B = poly(dodecyl acrylate) (D) arms that amplify “conformational asymmetry” through two concerted effects: the mikto architecture and disparate block statistical segment lengths. Analyzing the self-assembly of LD2 and LD3 samples resulted in the discovery of two TCP phases, σ and A15, that remained stable to significantly higher A-block volume fractions as the number of B arms increased. Finally, these results experimentally establish the importance of conformational asymmetry and molecular architecture as powerful design tools for the self-assembly of block copolymers into non-classical phases.},
doi = {10.1021/acsmacrolett.0c00061},
journal = {ACS Macro Letters},
number = 3,
volume = 9,
place = {United States},
year = {2020},
month = {2}
}

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