Article
  • Infulence of Spacer and Degree of Esterification on Thermotropic Liquid Crystalline Properties of Amyloses Bearing Cholesteryl Group
  • Jeong SY, Ma YD
  • 스페이서와 에스터화도가 콜레스테릴 그룹을 지닌 아밀로오스들의 열방성 액정 특성에 미치는 영향
  • 정승용, 마영대
Abstract
Three kinds of amylose derivatives such as: cholesteryloxycarbonated amyloses(CAMs) with degree of esterification(DE) ranging from 1.8 to 3, (6-cholesteryloxycarbonyl)pentanoated amyloses(PAMs) with DE ranging from 0.3 to 3, and fully cholesteryloxycarbonated PAMs(CPAMs) were synthesized, and their thermotropic liquid crystalline properties were investigated. CAMs with DE≥2.6, PAM with DE=1.6 and all the CPAMs formed enantiotropic cholesteric phases, whereas PAM with DE≥2.2 exhibited monotropic cholesteric phases. PAM with DE≥2.2 and CPAMs with (6-cholesteryloxycarbonyl)pentanoyl DE(DS) more than 1.0 formed cholesteric phases with left-handed helical structures whose optical pitches ( m,s) decrease with increasing temperature. However, the m,s of these samples decreased with increasing DS at the same temperature. On the other hand, CAMs, PAM with DE＝1.6, and CPAM with DS＝0.3 did not display reflection colors over the full cholesteric range, suggesting that the helicoidal twisting power of the cholesteryl group highly depends on the length of the spacer joining the cholesteryl group to the main chain and DS. The thermal stability and degree of order in the mesophase observed for the amylose derivatives highly depended on DE or DS. The results were discussed in terms of the difference in the hydrogen bond, the internal plasticization, and the decoupling of the motion of side group with the main chain.

세 종류의 아밀로오스 유도체들, 즉 에스터화도(DE)가 1.8에서 3의 범위에 있는 콜레스테릴옥시카본화 아밀로오스들(CAMs), DE가 0.3에서 3의 범위에 있는 (6-콜레스테릴옥시카보닐)펜타노화 아밀로오스들(PAMs), 그리고 완전치환 콜레스테릴옥시카본화 PAMs(CPAMs)들을 합성함과 동시에 이들의 열방성 액정 특성들을 검토하였다. DE≥2.6인 CAMs, DE=1.6인 PAM 그리고 모든 CPAMs는 쌍방성 콜레스테릭 상들을 형성하는 반면 DE≥2.2인 PAMs는 단방성 콜레스테릭 상들을 형성하였다. DE≥2.2인 PAMs 그리고 (6-콜레스테릴옥시카보닐)펜타노일 DE(DS)가 1.0 이상인 CPAMs는 온도상승에 의해 광학피치들( m,s)이 감소하는 콜레스테릭 상들을 형성하였다. 그러나 이들의 시료가 동일한 온도에서 나타내는 m은 DS가 증가함에 따라 감소하였다. 한편, CAMs, DE=1.6인 PAM 그리고 DS＝0.3인 CPAM은 콜레스테릭 상의 전 범위에서 반사색깔을 나타내지 않았다. 이러한 사실은 콜레스테릴 그룹에 의한 나선의 비틀림력은 콜레스테릴 그룹과 주사슬을 연결하는 스페이서의 길이와 DS에 민감하게 의존함을 시사한다. 아밀로오스 유도체들에서 관찰되는 콜레스테릭 상들의 열적 안정성 그리고 질서도는 DE 혹은 DS에 민감하게 의존하였다. 이들의 결과를 수소결합력, 주사슬의 가소화 그리고 주사슬로부터 곁사슬 그룹의 운동의 탈리의 차이와의 관련하에서 검토하였다.

Keywords: amylose; cholesterol; degree of esterification; temperature dependence of optical pitch; helicoidal sense

References
  • 1. Perce V, Pugh CSide Chain Liquid Crystal Polymers, C. B. McArdle, Editor, Chapmann and Hall, New York, Chap. 3, p. 30 (1989)
  •  
  • 2. Zentel RHandbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, and H.-W. Spiess, V. Vill, Editor, Wiley-VCH, Weinheim-New York, Vol. 3, Chap.Ⅰ, p. 52 (1998)
  •  
  • 3. Percec V, Asandei AD, Hill DH, Crawford D, Macromolecules, 32(8), 2597 (1999)
  •  
  • 4. Stumpe J, Fischer T, Menzel H, Macromolecules, 29(8), 2831 (1996)
  •  
  • 5. Chen BQ, Kameyama A, Nishikubo T, Macromolecules, 32(20), 6485 (1999)
  •  
  • 6. Piao XL, Kim JS, Yun YK, Jin JI, Hong SK, Macromolecules, 30(8), 2294 (1997)
  •  
  • 7. Lee JW, Jin JI, Jo BW, Kim JS, Zin WC, Kang, YS, Acta Polym., 50, 399 (1999)
  •  
  • 8. Cha SW, Jin JI, Kim DC, Zin WC, Macromolecules, 34(15), 5342 (2001)
  •  
  • 9. Fukuda T, Tsujii Y, Miyamoto T, Macromol. Symp., 99, 257 (1995)
  •  
  • 10. Ma YD, Polym. Sci. Technol., 8(5), 555 (1997)
  •  
  • 11. Zugenmaier PHandbook 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)
  •  
  • 12. Jeong SY, Jeong JH, Ma YD, Tsujii Y, Polym.(Korea), 25(2), 279 (2001)
  •  
  • 13. Zhou Q, Zhang LN, Okamura H, Minoda M, Miyamoto T, J. Polym. Sci. A: Polym. Chem., 39(3), 376 (2001)
  •  
  • 14. Yue ZL, Cowie JMG, Macromolecules, 35(17), 6572 (2002)
  •  
  • 15. Kim JH, Jeong SY, Ma YD, Polym.(Korea), 28(1), 92 (2004)
  •  
  • 16. Kim JH, Jeong SY, Ma YD, Polym.(Korea), 28(1), 41 (2004)
  •  
  • 17. Jeong SY, Ma YD, Polym.(Korea), 30(4), 338 (2006)
  •  
  • 18. Jeong SY, Ma YD, Polym.(Korea), 31(1), 37 (2007)
  •  
  • 19. Ma YD, Jeong SYPolymer Preprint, IUPAC-PSK30, 940 (2006)
  •  
  • 20. Shaikh VAE, Maldar NN, Lonikar SV, Rajan CR, Ponrathnam S, J. Appl. Polym. Sci., 70(1), 195 (1998)
  •  
  • 21. Shaikh VAE, Maldar NN, Lonikar SV, Rajan CR, Pontrathnam S, J. Appl. Polym. Sci., 72(6), 763 (1999)
  •  
  • 22. Wu C, Gu Q, Huang Y, Chen S, Liq. Cryst., 30, 733 (2003)
  •  
  • 23. Mihara T, Uedaira T, Koide N, Liq. Cryst., 29, 855 (2002)
  •  
  • 24. Hu JS, Zhang BY, Jia YG, Wang Y, Polym. J., 35, 160 (2003)
  •  
  • 25. Sainath AVS, Rao AK, Reddy AVR, J. Appl. Polym. Sci., 75(4), 465 (2000)
  •  
  • 26. Jeong SY, Ma YD, Polym.(Korea), 30(1), 35 (2006)
  •  
  • 27. Jeong SY, Ma YD, Polym.(Korea), 31(1), 58 (2007)
  •  
  • 28. Guo JX, Gray DG, Macromolecules, 22, 2082 (1989)
  •  
  • 29. Thies JC, Cowie JMG, Polymer, 42(4), 1297 (2001)
  •  
  • 30. Jeong SY, Choi JH, Ma YD, Polym.(Korea), 26(4), 523 (2002)
  •  
  • 31. Jeong SY, Ma YDto be pulished
  •  
  • 32. Pugh C, Kiste ALHandbook 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)
  •  
  • 33. Finkelmann H, Ringsdorf H, Siol W, Wendorff JH, Macromol. Chem., 179, 829 (1978)
  •  
  • 34. Freizon YS, Shibaev VPLiquid-Crystal Polymers, N. A. Plate, Editor, Plenum Press, New York, Chap. 7, p. 251 (1993)
  •  
  • 35. Weidner S, Wolff D, Springer J, Liq. Cryst., 20, 587 (1996)
  •  
  • 36. Weidner S, Wolft D, Springer J, Liq. Cryst., 22, 193 (1997)
  •  
  • 37. Bobrosky AY, Boiko NI, Shibaev VP, Liq. Cryst., 25, 679 (1998)
  •  
  • 38. Bobrosky AY, Boiko NI, Shibaev VP, Liq. Cryst., 27, 57 (2000)
  •  
  • 39. Hattori H, Uryu T, J. Polym. Sci. A: Polym. Chem., 38(5), 887 (2000)
  •  
  • 40. Kaneko T, Nagasawa H, Gong JP, Osada Y, Macromolecules, 37(1), 187 (2004)
  •  
  • 41. Barmatov EB, Barmatova MV, Moon BS, Park JG, Macromolecules, 37(15), 5490 (2004)
  •  
  • 42. Hu JS, Zhang BY, Liu ZJ, Zang BL, J. Appl. Polym. Sci., 86(11), 2670 (2002)
  •  
  • 43. Zhang BY, Hu JS, Jia YG, Du BG, Macromol. Chem. Phys., 204, 2123 (2003)
  •  
  • 44. Hu JS, Zhang BY, Jia YG, Chen S, Macromolecules, 36(24), 9060 (2003)
  •  
  • 45. Hu JS, Zhang BY, Wang Y, Meng FB, J. Polym. Sci. A: Polym. Chem., 42(15), 3870 (2004)
  •  
  • 46. Zang BL, Hu JS, Meng FB, Zhang BY, J. Appl. Polym. Sci., 93(6), 2511 (2004)
  •  
  • 47. Hu JS, Zhang BY, Yan G, He XZ, J. Polym. Sci. A: Polym. Chem., 42(20), 5262 (2004)
  •  
  • 48. Pfeutter T, Hanft D, Strohriegl P, Liq. Cryst., 29, 1555 (2002)
  •  
  • 49. Del Campo A, Meyer A, Perez E, Bello A, Liq. Cryst., 31, 109 (2004)
  •  
  • 50. Branolenburger F, Mattes B, Seifert K, Strohriegl P, Liq. Cryst., 28, 1035 (2001)
  •  
  • 51. Isogai A, Ishizu A, Nakano J, J. Appl. Polym. Sci., 29, 2097 (1984)
  •  
  • 52. Wu CC, Huang Y, Chen SX, Polym. Bull., 48(1), 33 (2002)
  •  
  • 53. Ma YD, Takada A, Sugiura M, Fukuda T, Miyamoto T, Watanabe J, Bull. Chem. Jpn., 67, 346 (1994)
  •  
  • 54. Yamaguchi T, Asada T, Hayashi H, Nakamura N, Macromolecules, 22, 1141 (1989)
  •  
  • 55. Lam JWY, Kong XX, Dong YP, Cheuk KKL, Xu KT, Tang BZ, Macromolecules, 33(14), 5027 (2000)
  •  
  • 56. Craig AA, Imrie CT, Macromolecules, 28(10), 3617 (1995)
  •  
  • 57. Pugh C, Kiste ALHandbook 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)
  •  
  • 58. Imrie CT, Karasz FE, Attard GS, Macromolecules, 26, 545 (1993)
  •  
  • 59. Craig AA, Imrie CT, Macromolecules, 32(19), 6215 (1999)
  •  
  • 60. Kim KH, Jeong SY, Ma YD, Polym.(Korea), 25(4), 545 (2001)
  •  
  • 61. Ogawa H, Stibal-Fischer E, Finkelmann H, Macromol. Chem. Phys., 205, 593 (2004)
  •  
  • 62. Liu LM, Zhang BY, Cheng CS, Zheng YY, J. Appl. Polym. Sci., 91(2), 773 (2004)
  •  
  • 63. Coles HHandbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinheim-New York, Vol. 2A, Chap. Ⅳ, p. 335 (1998)
  •  
  • 64. Jeong SY, Ma YD, Chem. Mater.(Dankook University), 3, 29 (2006)
  •  
  • 65. Tsai ML, Chen SH, Macromolecules, 23, 1908 (1990)
  •  
  • 66. Chen SH, Tsai ML, Macromolecules, 23, 5055 (1990)
  •  
  • 67. Krishnamurthy S, Chen SH, Macromolecules, 24, 3481 (1991)
  •  
  • 68. Kim JH, Jeong SY, Ma YD, Industrial Technology Research Paper(Dankook University), 7, 75 (2006)
  •  
  • 69. Vires HD, Acta Crystallogr., 4, 219 (1951)
  •  
  • 70. Yamagishi TA, Guittard F, Godinho MH, Martins AF, Cambon A, Sixou P, Polym. Bull., 32(1), 47 (1994)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2007; 31(4): 356-367

    Published online Jul 25, 2007

  • Received on May 17, 2007
  • Accepted on Jun 29, 2007