| Peer-Reviewed

Orientational Behavior of Liquid-Crystalline Polymers with Amide Groups

Received: 7 December 2014     Accepted: 25 December 2014     Published: 6 January 2015
Views:       Downloads:
Abstract

Liquid-crystalline polyacrylamides with mesogenic side-chains were synthesized by the radical polymerization of a mesogenic acrylamide derivative. Their thermal properties and orientational behavior were examined by polarizing microscopy, differential scanning calorimetry, temperature-variable IR, and X-ray diffraction measurements. The liquid-crystalline polyacrylamides containing secondary amide groups formed smectic A and smectic B phases during heating and cooling processes. The glass-smectic B, smectic B-A, and smectic A-isotropic phase transition temperatures increased with increasing molecular weight. The liquid-crystalline polyacrylamide showed higher phase transition temperatures than a liquid-crystalline polyacrylate, in which the secondary amide group was replaced with an ester group. The X-ray diffraction pattern of a smectic B-oriented sample of the liquid-crystalline polyacrylamide consisted of sharp inner and very sharp outer reflections. The very sharp reflection in the wide-angle region of the X-ray diffraction pattern indicated the formation of hexatic packing within the layer. The relationship between the layer distance and the extended mesogenic side-chain length suggested that the liquid-crystalline polyacrylamide formed an interdigitated bilayer structure. The IR spectra of the liquid-crystalline polyacrylamide exhibited that the number of hydrogen bonds between the secondary amide groups decreased with increasing temperature. In the liquid-crystalline polyacrylamide, smectic A and smectic B phases, with enhanced thermal stability, were formed through the formation of hydrogen bonds between the secondary amide groups.

Published in Advances in Materials (Volume 3, Issue 6)
DOI 10.11648/j.am.20140306.14
Page(s) 89-93
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2015. Published by Science Publishing Group

Keywords

Liquid Crystal Polymer, Amide, Urethane, IR, Hydrogen Bonding

References
[1] V. P. Shivaev, “Liquid-Crystalline Polymers: Past, Present, and Future”, Polym. Sci., Ser. A, vol. 51, 2009, pp. 1131-1193.
[2] P. J. Collings and J. S. Pate, Eds. Handbook of Liquid Crystal Research, New York: Oxford University Press, 1997, pp. 330-336.
[3] S. Ujiie and K. Iimura, “Thermal Properties and Orientational Behavior of a Liquid-Crystalline Ion Complex Polymer”, Macromolecules, vol. 25, 1992, pp. 3174-3178.
[4] S. Ujiie and K. Iimura, “Formation of Smectic Orientational Order in an Ionic Thermotropic Liquid-Crystalline Side-Chain Polymer”, Polym. J., vol. 25, 1993, pp. 347-354.
[5] T. Kojo, M. Nata, and S. Ujiie, “Liquid-Crystalline Binary Systems with Nonmesomorphic Comb-Shaped Polymer Component”, Mol. Cryst. Liq. Cryst., vol. 563, 2012, pp. 75-82.
[6] S. Ujiie, H. Uchino, and K. Iimura, “Induced Smectic Phase Formed by New Liquid Crystalline Binary Systems Consisting of Main Chain Polymer and Twin Compound” Chem. Lett., 1994, pp. 195-196.
[7] S. Ujiie, H. Uchino, and K. Iimura, “Induced Smectic A and C Phases Formed by Liquid-Crystalline Binary Systems Consisting of Nematic Twin Compounds”, J. Mater. Chem., vol. 5, 1995, pp.2229-2232.
[8] S. Ujiie, K. Maekawa, and K. Iimura, “Phase Transitions of Liquid Crystalline Polyacrylamide”, Mol. Cryst. Liq. Cryst., vol. 237, 1993, pp. 487-490.
[9] S. Ujiie and K. Iimura, “Thermal Properties and Orientational Behavior of Nematic Comb-Like Polyether”, Polym. J., vol. 24, 1992, pp. 427-431.
[10] S. Ujiie, Y. Tanaka, and K. Iimura, “Thermal and Liquid Crystalline Properties of Liquid Crystalline Polymethacrylates with Ammonium Units and their Non-ionic Family”, Polym. Adv. Technol., vol.11, 2000, pp. 450-455.
[11] H. Stevens, G. Rehage, and H. Finkelmann, “Phase Transformations of Liquid Crystalline Side-Chain Oligomers”, Macromolecules, vol.17, 1984, pp. 851-856.
[12] C. B. McArdle, Ed. Side Chain Liquid Crystal Polymers, New York: Chapman and Hall, 1989, pp. 54-56.
[13] S. Ujiie, G. Shimada, and M. Nata, “New Reactive Liquid-Crystalline Poly(aminourethane)s and Their Metal-Complexed Family”, Chem. Lett., in press.
[14] F.-S. Yen, L.-L. Lin, and J.-L. Hong, “Hydrogen-Bond Interactions between Urethane-Urethane and Urethane-Ester Linkages in a Liquid Crystalline Poly(ester-urethane)”, Macromolecules, vol. 32, 1999, pp. 3068-3079.
[15] L. Frang, H. Zhang, Z. Li, Y. Zhang, and H. Zhang, “Synthesis of Reactive Azobenzene Main-Chain Liquid Crystalline Polymers via Michael Addition Polymerization and Photomechanical Effects of Their Supramolecular Hydrogen-Bonded Fibers”, Macromolecules, vol. 46, 2013, pp. 7650-7660.
[16] A. Martinez-Felipe, C. T. Imrie, and A. Ribes-Greus, “Study of Formation in Side-Chain Liquid Crystal Copolymers by Variable Temperature Fourier Transform Infrared Spectroscopy”, Ind. Eng. Chem. Res., vol. 52, 2013, pp. 8714-8721.
Cite This Article
  • APA Style

    Genichiro Shimada, Masanori Nata, Shiori Tomitaka, Seiji Ujiie. (2015). Orientational Behavior of Liquid-Crystalline Polymers with Amide Groups. Advances in Materials, 3(6), 89-93. https://doi.org/10.11648/j.am.20140306.14

    Copy | Download

    ACS Style

    Genichiro Shimada; Masanori Nata; Shiori Tomitaka; Seiji Ujiie. Orientational Behavior of Liquid-Crystalline Polymers with Amide Groups. Adv. Mater. 2015, 3(6), 89-93. doi: 10.11648/j.am.20140306.14

    Copy | Download

    AMA Style

    Genichiro Shimada, Masanori Nata, Shiori Tomitaka, Seiji Ujiie. Orientational Behavior of Liquid-Crystalline Polymers with Amide Groups. Adv Mater. 2015;3(6):89-93. doi: 10.11648/j.am.20140306.14

    Copy | Download

  • @article{10.11648/j.am.20140306.14,
      author = {Genichiro Shimada and Masanori Nata and Shiori Tomitaka and Seiji Ujiie},
      title = {Orientational Behavior of Liquid-Crystalline Polymers with Amide Groups},
      journal = {Advances in Materials},
      volume = {3},
      number = {6},
      pages = {89-93},
      doi = {10.11648/j.am.20140306.14},
      url = {https://doi.org/10.11648/j.am.20140306.14},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.am.20140306.14},
      abstract = {Liquid-crystalline polyacrylamides with mesogenic side-chains were synthesized by the radical polymerization of a mesogenic acrylamide derivative. Their thermal properties and orientational behavior were examined by polarizing microscopy, differential scanning calorimetry, temperature-variable IR, and X-ray diffraction measurements. The liquid-crystalline polyacrylamides containing secondary amide groups formed smectic A and smectic B phases during heating and cooling processes. The glass-smectic B, smectic B-A, and smectic A-isotropic phase transition temperatures increased with increasing molecular weight. The liquid-crystalline polyacrylamide showed higher phase transition temperatures than a liquid-crystalline polyacrylate, in which the secondary amide group was replaced with an ester group. The X-ray diffraction pattern of a smectic B-oriented sample of the liquid-crystalline polyacrylamide consisted of sharp inner and very sharp outer reflections. The very sharp reflection in the wide-angle region of the X-ray diffraction pattern indicated the formation of hexatic packing within the layer. The relationship between the layer distance and the extended mesogenic side-chain length suggested that the liquid-crystalline polyacrylamide formed an interdigitated bilayer structure. The IR spectra of the liquid-crystalline polyacrylamide exhibited that the number of hydrogen bonds between the secondary amide groups decreased with increasing temperature. In the liquid-crystalline polyacrylamide, smectic A and smectic B phases, with enhanced thermal stability, were formed through the formation of hydrogen bonds between the secondary amide groups.},
     year = {2015}
    }
    

    Copy | Download

  • TY  - JOUR
    T1  - Orientational Behavior of Liquid-Crystalline Polymers with Amide Groups
    AU  - Genichiro Shimada
    AU  - Masanori Nata
    AU  - Shiori Tomitaka
    AU  - Seiji Ujiie
    Y1  - 2015/01/06
    PY  - 2015
    N1  - https://doi.org/10.11648/j.am.20140306.14
    DO  - 10.11648/j.am.20140306.14
    T2  - Advances in Materials
    JF  - Advances in Materials
    JO  - Advances in Materials
    SP  - 89
    EP  - 93
    PB  - Science Publishing Group
    SN  - 2327-252X
    UR  - https://doi.org/10.11648/j.am.20140306.14
    AB  - Liquid-crystalline polyacrylamides with mesogenic side-chains were synthesized by the radical polymerization of a mesogenic acrylamide derivative. Their thermal properties and orientational behavior were examined by polarizing microscopy, differential scanning calorimetry, temperature-variable IR, and X-ray diffraction measurements. The liquid-crystalline polyacrylamides containing secondary amide groups formed smectic A and smectic B phases during heating and cooling processes. The glass-smectic B, smectic B-A, and smectic A-isotropic phase transition temperatures increased with increasing molecular weight. The liquid-crystalline polyacrylamide showed higher phase transition temperatures than a liquid-crystalline polyacrylate, in which the secondary amide group was replaced with an ester group. The X-ray diffraction pattern of a smectic B-oriented sample of the liquid-crystalline polyacrylamide consisted of sharp inner and very sharp outer reflections. The very sharp reflection in the wide-angle region of the X-ray diffraction pattern indicated the formation of hexatic packing within the layer. The relationship between the layer distance and the extended mesogenic side-chain length suggested that the liquid-crystalline polyacrylamide formed an interdigitated bilayer structure. The IR spectra of the liquid-crystalline polyacrylamide exhibited that the number of hydrogen bonds between the secondary amide groups decreased with increasing temperature. In the liquid-crystalline polyacrylamide, smectic A and smectic B phases, with enhanced thermal stability, were formed through the formation of hydrogen bonds between the secondary amide groups.
    VL  - 3
    IS  - 6
    ER  - 

    Copy | Download

Author Information
  • Division of Materials Science and Production Engineering, Graduate School of Engineering, Oita University, Oita 870-1192, Japan

  • Department of Applied Chemistry, Faculty of Engineering, Oita University, Oita 870-1192, Japan

  • Department of Applied Chemistry, Faculty of Engineering, Oita University, Oita 870-1192, Japan

  • Department of Applied Chemistry, Faculty of Engineering, Oita University, Oita 870-1192, Japan

  • Sections