Synthesis of Liquid-Crystalline Polymer Containing Coumarin Moieties by Photopolymerization

Coumarin이 함유된 액정고분자의 광중합

  • Received : 2010.10.07
  • Accepted : 2010.12.17
  • Published : 2010.12.31

Abstract

Liquid-crystalline (LC) monomer, which was functionalized with a coumarin group on their extremity, was synthesized by UV light irradiation in their LC phases. LC monomer was converted into the dimers by the cycloaddition reaction of the coumarin group, and the LC phases were maintained after photodimerization reaction. The dimers showed LC phases in the wider temperature range than those of the corresponding monomer. Structures of the compound were identified by FT IR and $^1H$ NMR spectroscopies. Their phase transition temperatures and thermal stability were also investigated by differential scanning calorimetry (DSC), gel permeating chromatography (GPC) and polarized optical microscopy (POM). From optical polarizing microscopy, the prepared polymer shows enantiotropic liquid crystallinity with smectic and nematic textures.

Coumarin기가 포함된 액정성을 가진 단량체를 액정 상태에서 UV 조사에 의해 중합하였다. Cycloaddition 반응에 의해 coumarin 액정 단량체는 이량체로 전환되었으며, 광이량화 반응 후에도 액정성이 유지되었다. 그리고 이러한 이량체는 단량체의 액정범위 보다 넓은 영역에서 액정성을 나타내었다. 화합물의 구조는 FT IR 및 $^1H$ NMR에 의해 확인하였으며, 그들의 열적 상전이온도 및 열안정성들은 DSC, GPC 및 편광현미경에 의해 조사하였다. 광중합에 의해 생성된 고분자 생성물은 광학 편광 현미경 관찰에 의해 스멕틱 및 네마틱 조직을 갖는 쌍방성 액정성을 보였다.

Keywords

References

  1. 이신두, "액정" 전파과학사 (1994).
  2. 최이준, 진정일 "액정고분자" 문운당 (2001).
  3. J. Salamone, "Polymetric Materials", ed. by C. D. Eisenbach, p. 6957, Boca Raton, New York (1996).
  4. P. J. Collings, "Liquid crystals", ed. by P. J. Collings, P. 3, Princeton University Press (1990).
  5. P. J. Collings, M. Hird, "Introduction to Liquid crystals", Taylor & Francis Ltd, London (1997).
  6. J. I. Jin, S. Antoun, C. Ober, and R. W. Lenz, "Thermotropic Liquid Crystalline Polyesters with Rigid or Flexible Spacer Groups", Polym. J., 12, 132 (1980).
  7. H. Kihara, and N. Tamaoki, "In situ Photochemical Conversion from Cinnamoyl-functionalized Liquid-Crystalline Monomers to Liquid-Crystalline Dimers" Liquid Crystals, 34, 1337 (2007). https://doi.org/10.1080/02678290701697454
  8. R. S. Trenor, A. R. Shultz, B. J. Love, and T. E. Long, "Coumarins in Polymers: From Light Harvesting to Photo-Cross-Linkable Tissue Scaffolds" Chem. Rev., 104, 3059 (2004). https://doi.org/10.1021/cr030037c
  9. X. YU, D. Scheller, O. Rademacher, and T. Wolff, "Selectivity in the Photodimerization of 6-Alkylcoumarins" J. Org. Chem., 68, 7386 (2003). https://doi.org/10.1021/jo034627m
  10. N. K. Mal, M. Fujiwara and Y. Tanaka, "Photocontrolled Reversible Release of Gust Molecules from Coumarin-modified Mesoporous Silica" Nature, 421, 350, (2003). https://doi.org/10.1038/nature01362
  11. Y. Tian, E. Akiyama, Y. Nagase, A. Kanazawa, O. Tsutsumi, and T. Ikeda, "Liquid Crystalline Coumarin Polymers" Macromol. Chem. Phys., 201, 1640 (2000). https://doi.org/10.1002/1521-3935(20000901)201:14<1640::AID-MACP1640>3.0.CO;2-Z
  12. P. O. Jackson and M. O'Neill, "An Investigation of the Role of Cross-Linking and Photodegradation of side-Chain Coumarin Polymers in the Photoalignment of Liquid Crystals" Chem. Mater., 13, 694 (2001). https://doi.org/10.1021/cm0011413
  13. J. B. Lee, T. Kato, T. Yoshida, and T. Uryu, "Synthesis and Liquid Crystalline Properties of Thermotropic Polyurethanes Prepared from 1,4-Diisocyanates and 4,4'-Bis($\omega$-hydroxyalkoxy) biphenyls", Macromolecules, 26, 4989 (1993). https://doi.org/10.1021/ma00071a001
  14. J. B. Lee, T. Kato, S. Ujiie, K. Iimura, and T. Uryu, "Thermotropic Polyurethanes Prepared from 2,5-Tolylene Diisocyanates and 1,4-Bis($\omega\$-hydroxyalkoxy)benzenes Containing No Mesogenic Unit", Macromolecules, 28, 2165 (1995). https://doi.org/10.1021/ma00111a010
  15. D. J. Lee, J. B. Lee, N. Koide, E. Akiyama, and T. Uryu, "Liquid Crystallinity of Thermotropic Para-Type Home- and Copolyurethanes containing Biphenylene Mesogen and Their Blends", Macromolecules, 31, 975 (1998). https://doi.org/10.1021/ma970866y
  16. H. M. Jeong, J. B. Lee, S. Y. Lee, and B. K. Kim, "Shape Memory Polyurethane Containing Mesogenic Moiety", J. of Materials Sci., 35, 279 (2000). https://doi.org/10.1023/A:1004728814128
  17. J. B. Lee, "Thermal Properties of Liquid-Crystalline Polyurethanes Containing Biphenylene Mesogen", Key Engin. Mater., 321, 1385 (2006).
  18. S. R. Trenor, T. E. Long and B. J. Love, "Photoreversible Chain Extension of Poly(ethylene glycol)", Macromolecular Chem. and Phys., 205, 715 (2004). https://doi.org/10.1002/macp.200300168
  19. H. kihara and N. Tamaoki, "A Main-Chain Liquid-Crystalline Oligomer Prepared by in situ Photopolymerization of an LC Monomer Having Cinnamate Moieties", MacromolecularRapid Communications, 27, 829 (2006).
  20. Y. Tian, E. Akiyama, Y. Nagase, A. Kanazawa, O. Tsutsumi and T. Ikeda, "Liquid Crystalline Coumarin Polymers", Macromol. Chem. Phys., 201, 1640 (2000). https://doi.org/10.1002/1521-3935(20000901)201:14<1640::AID-MACP1640>3.0.CO;2-Z
  21. J. B. Lee, K. C. Lee, D. J Lee and H. Kihara, "Synthesis and Characterization of New Main Chain Liquid Crystalline Coumarin Compound with Ester Moiety", Elastomer and Composites, 44, 416 (2009).