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Title: Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush

Abstract

Grafting density is an important structural parameter that imparts significant influences over the physical properties of architecturally complex polymers. In this paper, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization (ROMP). ω-norbornenyl poly(D,L-lactide) (PLA) and polystyrene (PS) macromonomers were copolymerized with discrete co-monomers in different feed ratios, enabling precise control over the grafting density. Small-angle X-ray scattering (SAXS) experiments demonstrate that these graft block polymers can self-assemble into long-range-ordered lamellar structures. For seventeen series of block polymers with variable z, the scaling of the lamellar period with the total backbone degree of polymerization (d* ~ N bb α) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, instead of segregation strengths. Amore » model is pro-posed in which the characteristic ratio (C ), a proxy for the backbone stiffness, scales with N bb as a function of the grafting density: C ~ N bb f(z). To the best of our knowledge, this report represents the first study of scaling behavior for the self-assembly of block polymers with variable grafting density. Lastly, the relationships disclosed herein provide valuable insights into conformational changes with grafting density, thus introducing new opportunities for future block polymer design.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division, Advanced Photon Source
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1416003
Grant/Contract Number:  
AC02-06CH11357; AR0000683
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 11; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block polymer; bottlebrush; graft polymer; lamellae; scaling; self-assembly

Citation Formats

Lin, Tzu-Pin, Chang, Alice B., Luo, Shao-Xiong, Chen, Hsiang-Yun, Lee, Byeongdu, and Grubbs, Robert H. Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b06664.
Lin, Tzu-Pin, Chang, Alice B., Luo, Shao-Xiong, Chen, Hsiang-Yun, Lee, Byeongdu, & Grubbs, Robert H. Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush. United States. doi:10.1021/acsnano.7b06664.
Lin, Tzu-Pin, Chang, Alice B., Luo, Shao-Xiong, Chen, Hsiang-Yun, Lee, Byeongdu, and Grubbs, Robert H. Thu . "Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush". United States. doi:10.1021/acsnano.7b06664.
@article{osti_1416003,
title = {Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush},
author = {Lin, Tzu-Pin and Chang, Alice B. and Luo, Shao-Xiong and Chen, Hsiang-Yun and Lee, Byeongdu and Grubbs, Robert H.},
abstractNote = {Grafting density is an important structural parameter that imparts significant influences over the physical properties of architecturally complex polymers. In this paper, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization (ROMP). ω-norbornenyl poly(D,L-lactide) (PLA) and polystyrene (PS) macromonomers were copolymerized with discrete co-monomers in different feed ratios, enabling precise control over the grafting density. Small-angle X-ray scattering (SAXS) experiments demonstrate that these graft block polymers can self-assemble into long-range-ordered lamellar structures. For seventeen series of block polymers with variable z, the scaling of the lamellar period with the total backbone degree of polymerization (d* ~ Nbbα) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, instead of segregation strengths. A model is pro-posed in which the characteristic ratio (C∞), a proxy for the backbone stiffness, scales with Nbb as a function of the grafting density: C∞ ~ Nbbf(z). To the best of our knowledge, this report represents the first study of scaling behavior for the self-assembly of block polymers with variable grafting density. Lastly, the relationships disclosed herein provide valuable insights into conformational changes with grafting density, thus introducing new opportunities for future block polymer design.},
doi = {10.1021/acsnano.7b06664},
journal = {ACS Nano},
number = 11,
volume = 11,
place = {United States},
year = {Thu Oct 26 00:00:00 EDT 2017},
month = {Thu Oct 26 00:00:00 EDT 2017}
}

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