Tacticity Effect on Mesogen-Free Liquid Crystalline Self-assembly Induced by Strong Dipole–Dipole Interactions
Abstract
Strong dipole–dipole interactions in mesogen-free aliphatic comblike polymers can induce unique liquid crystalline (LC) self-assembly. By comparing atactic and isotactic poly(oxypropylene)s with n-alkylsulfonyl side groups (aPOP-SO2Cn and iPOP-SO2Cn), the effect of main-chain tacticity on the ordered phase behavior was studied in this work. For aPOP-SO2Cn, LC self-assemblies were observed when n is ≥3. Two types of LC phases were formed depending on the side chain length n: (i) a three-dimensional (3D) high-order LC structure (possibly crystal B or E) for n = 3–5 and (ii) a smectic A (SmA) structure for n = 6–12. For iPOP-SO2Cn, crystallization was favored as a result of regular main-chain configuration. Only when n ≥ 10, the isotactic comblike polymers exhibited a monotropic phase behavior with the SmA phase appearing during cooling from the isotropic melt. Regardless of atactic or isotactic main chains, these ordered LC and crystalline phases featured a double-layer structure, which was dictated by the optimal dipole–dipole interaction distance (i.e., 0.40–0.44 nm) between sulfonyl groups in the neighboring side chains. Here, this study showed that the chiral centers incorporated in the backbone could not induce chiral smectic self-assembly for the isotactic polymers. As such, we are currently implementing chiral centers in themore »
- Authors:
-
[2];
[1]
- Case Western Reserve Univ., Cleveland, OH (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States); Case Western Reserve Univ., Cleveland, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1524563
- Alternate Identifier(s):
- OSTI ID: 1899874
- Report Number(s):
- BNL-211749-2019-JAAM
Journal ID: ISSN 0024-9297
- Grant/Contract Number:
- SC0012704; SC0018075
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 52; Journal Issue: 10; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Chromatography; Liquid crystals; Phase transitions; Physical and chemical processes; Polymers
Citation Formats
Kwok, Man -Hin, Seymour, Bryan T., Li, Ruipeng, Litt, Morton H., Zhao, Bin, and Zhu, Lei. Tacticity Effect on Mesogen-Free Liquid Crystalline Self-assembly Induced by Strong Dipole–Dipole Interactions. United States: N. p., 2019.
Web. doi:10.1021/acs.macromol.9b00537.
Kwok, Man -Hin, Seymour, Bryan T., Li, Ruipeng, Litt, Morton H., Zhao, Bin, & Zhu, Lei. Tacticity Effect on Mesogen-Free Liquid Crystalline Self-assembly Induced by Strong Dipole–Dipole Interactions. United States. https://doi.org/10.1021/acs.macromol.9b00537
Kwok, Man -Hin, Seymour, Bryan T., Li, Ruipeng, Litt, Morton H., Zhao, Bin, and Zhu, Lei. Mon .
"Tacticity Effect on Mesogen-Free Liquid Crystalline Self-assembly Induced by Strong Dipole–Dipole Interactions". United States. https://doi.org/10.1021/acs.macromol.9b00537. https://www.osti.gov/servlets/purl/1524563.
@article{osti_1524563,
title = {Tacticity Effect on Mesogen-Free Liquid Crystalline Self-assembly Induced by Strong Dipole–Dipole Interactions},
author = {Kwok, Man -Hin and Seymour, Bryan T. and Li, Ruipeng and Litt, Morton H. and Zhao, Bin and Zhu, Lei},
abstractNote = {Strong dipole–dipole interactions in mesogen-free aliphatic comblike polymers can induce unique liquid crystalline (LC) self-assembly. By comparing atactic and isotactic poly(oxypropylene)s with n-alkylsulfonyl side groups (aPOP-SO2Cn and iPOP-SO2Cn), the effect of main-chain tacticity on the ordered phase behavior was studied in this work. For aPOP-SO2Cn, LC self-assemblies were observed when n is ≥3. Two types of LC phases were formed depending on the side chain length n: (i) a three-dimensional (3D) high-order LC structure (possibly crystal B or E) for n = 3–5 and (ii) a smectic A (SmA) structure for n = 6–12. For iPOP-SO2Cn, crystallization was favored as a result of regular main-chain configuration. Only when n ≥ 10, the isotactic comblike polymers exhibited a monotropic phase behavior with the SmA phase appearing during cooling from the isotropic melt. Regardless of atactic or isotactic main chains, these ordered LC and crystalline phases featured a double-layer structure, which was dictated by the optimal dipole–dipole interaction distance (i.e., 0.40–0.44 nm) between sulfonyl groups in the neighboring side chains. Here, this study showed that the chiral centers incorporated in the backbone could not induce chiral smectic self-assembly for the isotactic polymers. As such, we are currently implementing chiral centers in the side chains for the formation of ferroelectric structures for these mesogen-free aliphatic LC polymers.},
doi = {10.1021/acs.macromol.9b00537},
journal = {Macromolecules},
number = 10,
volume = 52,
place = {United States},
year = {Mon May 06 00:00:00 EDT 2019},
month = {Mon May 06 00:00:00 EDT 2019}
}
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