화학공학소재연구정보센터
Polymer(Korea), Vol.31, No.1, 37-46, January, 2007
6-[4-(4'-(니트로페닐아조)펜옥시카보닐)]펜타노화 다당류들의 합성과 열방성 액정 거동
Synthesis and Thermotropic Liquid Crystalline Behaviors of 6-[4-(4′-(nitrophenylazo)phenoxycarbonyl)]pentanoated Polysaccharides
E-mail:
초록
셀룰로오스, 아밀로오스, 키토산, 키틴, 알긴산, 풀루란 또는 아밀로펙틴을 6-[4-(4'-(니트로페닐아조)펜옥시)]펜타노일 클로라이드(NA6C)와 반응시켜 전치환 또는 거의 전치환 6-[4-(4'-(니트로페닐아조)펜옥시카보닐)]펜타노화 다당류 유도체들을 합성함과 동시에 이들의 열방성 액정의 거동들을 검토하였다. NA6C의 경우와 같이, 모든 다당류 유도체들은 단방성 네마틱 상들을 형성하였다. 이러한 사실은 다당류 유도체들의 액정 구조는 다당류 골격에 의해 결정되는 것이 아니고 mesogenic 곁사슬 그룹들에 의해 결정됨을 시사한다. 이것이 셀룰로오스 유도체들을 제외한 다당류 유도체들이 열방성 네마틱 상을 형성한다고 하는 최초의 보고이다. 다당류 유도체들에 있어서 관찰되는 네마틱 상들의 열적 안정성과 질서도는 아조벤젠 그룹들을 유연한 스페이서를 통하여 유연한 혹은 강직한 골격들에 도입시켜 얻은 고분자들에 대해 보고된 결과들과 현저히 다르다. 이들의 결과를 주사슬과 곁사슬의 배열 그리고 주사슬의 유연성의 차이와 관련하에서 검토하였다.
Fully or nearly fully 6-[4-(4'-(nitrophenylazo)phenoxycarbonyl)]pentanoated polysaccharide derivatives were synthesized by reacting cellulose, amylose, chitosan, chitin, alginic acid, pullulan or amylopectin with 6-[4-(4'-(nitrophenylazo)phenoxy)]pentanoyl chloride(NA6C) and their thermotropic liquid crystalline behaviors were investigated. Like in the case of NA6C, all the polysaccharide derivatives formed monotropic nematic phases, suggesting that the mesophase structure of the polysaccharide derivatives is dertermined by the mesogenic side groups and not by the polysaccharide backbone. This is the first report of polysaccharide derivatives, except cellulose derivative, that form thermotropic nematic phases. The thermal stability and degree of order of the nematic phases observed for polysaccharide derivatives were significantly different from those reported for the polymers in which the azobenzene groups are attached to flexible or rigid backbones through flexible spacers. The results were discussed in terms of the difference in the arrangement of the main and side chains and the flexibility of the main chain.
  1. Werbowyj RS, Gray DG, Mol. Cryst. Liq. Cryst., 34, 97 (1976)
  2. Fukuda T, Tsujii Y, Miyamoto T, Macromol. Symp., 99, 257 (1995)
  3. Ma YD, Polym. Sci. Technol., 8, 555 (1997)
  4. Zugenmair P, Handbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinheim-New York, Vol 3, Chap. Ⅸ, p 453 (1998)
  5. Ma YD, Kim KH, Polym.(Korea), 24(3), 418 (2000)
  6. Jeong SY, Jeong JH, Ma YD, Tsujii Y, Polym.(Korea), 25(2), 279 (2001)
  7. Zhou Q, Zhang LN, Okamura H, Minoda M, Miyamoto T, J. Polym. Sci. A: Polym. Chem., 39(3), 376 (2001)
  8. Yue ZL, Cowie JMG, Macromolecules, 35(17), 6572 (2002)
  9. Reck B, Ringsdorf H, Makromol. Chem. Rapid Commun., 6, 291 (1985)
  10. Percec V, Pugh C, Side Chain Liquid Crystal Polymers, C. B. McArdle, Editor, Chapman and Hall, New York, Chap. 3, p 30 (1989)
  11. Zentel R, Handbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinheim-New York, Vol 3, Chap. I, p 52 (1998)
  12. Chen BQ, Kameyama A, Nishikubo T, Macromolecules, 32(20), 6485 (1999)
  13. Percec V, Asandei AD, Hill DH, Crawford D, Macromolecules, 32(8), 2597 (1999)
  14. Stumpe J, Fischer T, Menzel H, Macromolecules, 29(8), 2831 (1996)
  15. Ge JJ, Zhang AQ, Mccreight KW, Ho RM, Wang SY, Jin XM, Harris FW, Cheng SZ, Macromolecules, 30(21), 6498 (1997)
  16. Piao XL, Kim JS, Yun YK, Jin JI, Hong SK, Macromolecules, 30(8), 2294 (1997)
  17. Lee JW, Jin JI, Jo BW, Kim JS, Zin WC, Kang YS, Acta Polym., 50, 399 (1999)
  18. Cha SW, Jin JI, Kim DC, Zin WC, Macromolecules, 34(15), 5342 (2001)
  19. Kumaresan S, Kannan P, J. Polym. Sci. A: Polym. Chem., 41(20), 3188 (2003)
  20. Sato M, Mizoi M, Uemoto Y, Macromol. Chem. Phys., 202, 3634 (2001)
  21. Sato M, Mizoi M, Polym. J., 36, 607 (2004)
  22. Huang WY, Han CD, Polymer, 47(12), 4400 (2006)
  23. Kim JH, Jeong SY, Ma YD, Polym.(Korea), 28(1), 92 (2004)
  24. Kim JH, Jeong SY, Ma YD, Polym.(Korea), 28(1), 41 (2004)
  25. Jeong SY, Ma YD, Polym.(Korea), 30(4), 338 (2006)
  26. Brehmer L, Polymer Sensors and Actuators, Y. Osada and D. E. DeRossi, Editors, Springer-Verlag, Berlin, Chap. 2, p 15 (2002)
  27. Pugh C, Kiste AL, Handbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinheim-New York, Vol 3, Chap. Ⅲ, p 123 (1998)
  28. Sapich B, Vix ABE, Rabe JP, Stumpe J, Macromolecules, 38(25), 10480 (2005)
  29. Chiellini E, Laus M, Handbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinheim-New York, Vol 3, Chap. Ⅰ, p 26 (1998)
  30. Kumaresan S, Kannan P, J. Appl. Polym. Sci., 91(1), 455 (2004)
  31. Alazaroaie S, Toader V, Carlescu I, Kazmierski K, Scutaru D, Hurduc N, Simionescu CI, Europ. Polym, J., 39, 1333 (2003)
  32. Sandhya KY, Pillai CKS, J. Appl. Polym. Sci., 91(3), 1976 (2004)
  33. Acierno D, Amendola E, Bugatti V, Concilio S, Giorgini L, Iannelli P, Piotto SP, Macromolecules, 37(17), 6418 (2004)
  34. Seki T, Polym. J., 36, 435 (2004)
  35. Bowry C, Processes in Photoreactive Polymers, V. V. Krongauz and A. D. Trifunac, Editors, Chapman & Hall, New York, Chap. 7, p 278 (1995)
  36. Martin PJ, Introduction to Molecular Electronics, M. C. Petty, M. R. Bryce, and D. Bloor, Editors, Edward Arnold, London, Chap. 6, p 112 (1995)
  37. Yashima E, Noguchi J, Okamoto Y, Macromolecules, 28(24), 8368 (1995)
  38. Okamoto Y, Sakamoto H, Hatada K, Irie M, Chem. Lett., 983 (1986)
  39. Muller M, Zentel R, Macromol. Chem. Phys., 201, 2055 (2002)
  40. Wu C, Gu Q, Huang Y, Chen S, Liq. Cryst., 30, 733 (2003)
  41. Buchel M, Weichart B, Minx C, Menzel H, Johannsmann D, Phys. Rev. E, 55, 455 (1997)
  42. Yang SZ, Jacob MM, Li L, Cholli AL, Kumar J, Tripathy SK, Macromolecules, 34(26), 9193 (2001)
  43. Zheng P, Hu X, Zhao X, Li L, Tam KC, Gan LH, Macromol. Rapid Commun., 25, 678 (2004)
  44. Hu X, Zheng PJ, Zhao XY, Li L, Tam KC, Gan LH, Polymer, 45(18), 6219 (2004)
  45. Zhou LM, Xu Q, Wang DN, J. Appl. Polym. Sci., 100(4), 2832 (2006)
  46. Kurihara S, Iwamoto K, Nonaka T, Polymer, 39(15), 3565 (1998)
  47. Lee SB, Yang JS, Park DK, Polym.(Korea), 25(4), 496 (2001)
  48. Liu JH, Wu FT, J. Appl. Polym. Sci., 97(3), 721 (2005)
  49. Lee JW, Jin JI, Achard MF, Hardouin F, Liq. Cryst., 28, 663 (2001)
  50. Ma YD, Jeong SY, Industrial Technology Research Paper(Dankook university), 5, 21 (2004)
  51. Kim SS, Kim SH, Lee YM, J. Polym. Sci. B: Polym. Phys., 34(14), 2367 (1996)
  52. Ma YD, Jeong SY, Jeong JH, Kim KH, Dankook University Faculty Research Papers, 33, 425 (1998)
  53. Sugiura M, Minoda M, Watanabe J, Fukuda T, Miyamoto T, Bull. Chem. Soc. Jpn., 65, 1939 (1992)
  54. Itoh T, Suzuki H, Miyamoto T, Bull. Inst. Chem. Res., Kyoto Univ., 70, 132 (1992)
  55. Aoi K, Takasu, Okada M, Macromol. Chem. Phys., 195, 3835 (1994)
  56. Kubota N, Eguchi Y, Polym. J., 29, 123 (1997)
  57. Liu JH, Yang PC, J. Appl. Polym. Sci., 91, 3693 (2004)
  58. Isogai A, Ishizu A, Nakano J, J. Appl. Polym. Sci., 30, 345 (1985)
  59. Lee JL, Pearce EM, Kwei TK, Macromolecules, 30(26), 8233 (1997)
  60. Noel C, Handbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinhein-New York, Vol 3, Chap. Ⅱ, p 93 (1998)
  61. Kong X, Tang BZ, Chem. Mater., 10, 3352 (1998)
  62. Lam JWY, Tang BZ, J. Polym. Sci. A: Polym. Chem., 41(17), 2607 (2003)
  63. Maganini P, Thermotropic Liquid Crystal Polymer Blends, F. P. La Mania, Editor, Technonic Publishing Company, Inc., Western Hemisphere, Chap. 1, p 1 (1993)
  64. Yalpani M, Polysaccharides, Elsevier, New York, Chap. 4, p 83 (1988)
  65. Oh CI, M. Sc. Dissertation, DanKook University, 1996. (b) H. Jeong, M. Sc. Dissertation, DanKook University (1997)
  66. Ma YD, Jeong SY, Industrial Technology Research Paper(Dankook University), 5, 21 (2004)
  67. Ma YD, Jeong SY, Industrial Technology Research Paper(Dankook University), 6, 1 (2005)
  68. Jeong SY, Ma YD, Polym.(Korea), 30(1), 35 (2006)
  69. Rath SK, Singh RP, J. Appl. Polym. Sci., 70(9), 1795 (1998)
  70. Xiao CB, Gao SJ, Zhang LN, J. Appl. Polym. Sci., 77(3), 617 (2000)
  71. Athawale VD, Rathi SC, Eur. Polym. J., 33, 1067 (1997)
  72. Xiao CB, Lu YS, Liu HJ, Zhang L, J. Appl. Polym. Sci., 80(1), 26 (2001)
  73. Vega D, Villar MA, Failla MD, Valles EM, Polym. Bull., 37, 229 (1996)
  74. Vigo TL, Encyclopeida of Polymer Science and Engineering, H. F. Mark, N. M. Bikales, C. G. Overberger, G. Menges, and J. I. Kroschwitz, Editors, Jhon Wiley & Sons, Inc., Vol. 3, p 110 (1985)
  75. Qu X, Wirsen A, Albertsson AC, Polymer, 41(13), 4841 (2000)
  76. Sui Y, Liu YG, Yin J, Gao J, Zhu ZK, Huang DY, Wang ZG, J. Polym. Sci. A: Polym. Chem., 37(23), 4330 (1999)
  77. Ivanov S, Yakovlev I, Kostromin S, Shibaev V, Macromol. Chem., Rapid Commun., 12, 709 (1991)
  78. Tsutsumi O, Kitsunai T, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(2), 355 (1998)
  79. Wu YL, Zhang QJ, Kanazawa A, Shiono T, Ikeda T, Nagase Y, Macromolecules, 32(12), 3951 (1999)
  80. Han M, Ichimura K, Macromolecules, 34(1), 82 (2001)
  81. Han M, Ichimura K, Macromolecules, 34(1), 90 (2001)
  82. Andreozzi L, Camorani P, Faetti M, Palazzuoli D, Mol. Cryst. Liq. Cryst., 375, 129 (2002)
  83. Sasaki T, Kai R, Sato A, Ishikawa Y, Yoshimi T, Mol. Cryst. Liq. Cryst., 373, 53 (2002)
  84. Yoneyama S, Yamamoto T, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 35(23), 8751 (2002)
  85. Ikeda T, Yoneyama S, Hasegawa M, Mol. Cryst. Liq. Cryst., 401, 35 (2003)
  86. Tsutsumi O, Shiono T, Ikeda T, Galli G, J. Phys. Chem. B, 101(8), 1332 (1997)
  87. Wu YL, Demachi Y, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(2), 349 (1998)
  88. Wu YL, Demachi Y, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(14), 4457 (1998)
  89. Wu YL, Mamiya J, Kanazawa A, Shiono T, Ikeda T, Zhang QJ, Macromolecules, 32(26), 8829 (1999)
  90. Andruzzi L, Altomare A, Ciardelli F, Solaro R, Hvilsted S, Ramanujam PS, Macromolecules, 32(2), 448 (1999)
  91. Wu Y, Mamiya JI, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Liq. Cryst., 27, 749 (2000)
  92. Meier JG, Ruhmann R, Stumpe J, Macromolecules, 33(3), 843 (2000)
  93. Andreozzi L, Faetti M, Giordano M, Palazzuoli D, Laus M, Galli G, Macromol. Chem. Phys., 203, 1636 (2002)
  94. He XH, Zhang HL, Yan DY, Wang XY, J. Polym. Sci. A: Polym. Chem., 41(18), 2854 (2003)
  95. Andreozzi L, Faetti M, Polazzuoli D, Giordano M, Galli G, Mol. Cryst. Liq. Cryst., 398, 87 (2003)
  96. Xia T, Li C, Yue Z, Macromolecules, 37(9), 3101 (2004)
  97. Bo Q, Yavrian A, Galstian T, Zhao Y, Macromolecules, 38(8), 3079 (2005)
  98. Gimenez R, Millaruelo M, Pinol M, Serrano JL, Vinuales A, Rosenhauer R, Fischer T, Stumpe J, Polymer, 46(22), 9230 (2005)
  99. Liu JH, Hsieh CD, J. Appl. Polym. Sci., 99(5), 2443 (2006)
  100. Rosenhauer R, Fischer T, Stumpe J, Gimenez R, Pinol M, Serrano JL, Vinuales A, Broer D, Macromolecules, 38(6), 2213 (2005)
  101. Zheng Z, Xu J, Sun YY, Zhou JL, Chen B, Zhang QJ, Wang KY, J. Polym. Sci. A: Polym. Chem., 44(10), 3210 (2006)
  102. Hempel G, Dimitrova A, Lindau J, Reichert D, Schneider H, Macromol. Chem. Phys., 204, 674 (2003)
  103. He X, Yan D, Macromol. Rapid Commun., 25, 949 (2004)
  104. Hsu B, McWherter CA, Brant DA, Burchard W, Macromolecules, 15, 1350 (1982)