화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Polymer(Korea), Vol.32, No.5, 489-496, September, 2008
Export Citation
폴리[1-{4-(4′-니트로페닐아조)페녹시카보닐알카노일옥시}에틸렌]들의 열방성 액정 거동
Thermotropic Liquid Crystalline Behavior of Poly[1-{4-(4′-nitrophenylazo)phenoxycarbonylalkanoyloxy}ethylene]s
정승용, 마영대†
  • 단국대학교 고분자공학과, 경기도 용인시 수지구 죽전동 산126, 448-701
Seung Yong Jeong, and Yung Dae Ma†
  • Department of Polymer Science and Engineering, Dankook University, San 126, Jukjean-dong, Suji-gu, Yongin-si, Gyeongi-do 448-701, Korea
E-mail:
초록
폴리[1-{4-(4′-니트로페닐아조)페녹시카보닐알카노일옥시}에틸렌]들(NAPEn, n=2∼8,10, 유연격자 중의 메틸렌 단위들의 수)의 동족체들의 열방성 액정 거동을 검토하였다. 모든 동족체들은 단방성 네마틱 상들을 형성하였다. 유리전이온도들은 n이 증가함에 따라 낮아졌다. 이러한 사실은 곁사슬 그룹들에 의한 주사슬의 가소화에 의해 초래되는 것으로 생각된다. 액체 상에서 네마틱 상으로의 전이온도들은 n이 7까지는 낮아지며 홀수-짝수 효과를 나타냈다. 그러나 n>7인 동족체들의 전이온도는 거의 일정하게 되었다. 이러한 거동은 유연격자의 홀수-짝수의 변화에 기인한 곁사슬의 평균적인 형태변화의 견지에서 합리적으로 설명된다. 전이온도에서 관찰되는 엔트로피 증가의 변화도 동일한 관점에서 설명된다. NAPEn이 나타내는 액정 특성들은 폴리아크릴레이트, 폴리메타크릴레이트 그리고 폴리스틸렌에 아조벤젠 그룹들을 폴리메틸렌 유연격자들을 통하여 연결시켜 얻은 고분자들에 대해 보고된 결과와 전혀 달랐다. 이러한 결과들은 주사슬과 곁사슬의 화학적 결합양식이 액정상의 형성능, 안정성 그리고 구조에 중요한 역할을 함을 시사한다.
The thermotropic liquid crystalline behavior of a homologous series of poly[1-{4-(4′-nitrophenylazo)phenoxycarbonylalkanoyloxy}ethylene]s(NAPEn, n=2∼8,10, the number of methylene units in the spacer) have been investigated. All of the homologues formed monotropic nematic phases. The glass transition temperatures decreased with n. This is attributed to a plasticization of the backbone by the side chains. The isotropic-nematic phase transition temperatures decreased with increasing n up to 7 and showed the odd-even effect. However it became almost constant when n is more than 7. This behavior was rationalized in terms of the change in the average shape of the side chain on varing the parity of the spacer. This rationalization also accounts for the observed variation of the entropic gain for the clearing transition. The mesophase properties of NAPEn were entirely different from those reported for the polymers in which the azobenzene groups are attached to polyacrylate, polymathacrylate, and polystyrene backbones through polymethylene spacers. The results indicate that the mode of chemical linkage of the side group with the main chain plays an important role in the formation, stabilization, and type of mesophase.
Keywords:poly(vinyl alcohol);nitroazobenzene;spacer length;nematic phase;odd-even effect
  1. Xie S, Natansohn A, Rochon P, Chem. Mater., 5, 403 (1993)
  2. Shibaev V, Bobrovsky A, Boiko N, Prog. Polym. Sci, 28, 729 (2003)
  3. Brehmer L, Polymer Sensors and Actuator, Y. Osada and D. De Rossi, Editors, Springer-Verlag, Berlin, Chap 2, p 15 (2002)
  4. Imrie CT, Karasz FE, Attard GS, Macromolecules, 25, 1278 (1992)
  5. Imrie CT, Karasz FE, Attard GS, Macromolecules, 26, 545 (1993)
  6. 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)
  7. Li M, Zhou E, Xu JP, Chen XF, J. Appl. Polym. Sci., 60(12), 2185 (1996)
  8. Tsutsumi O, Shiono T, Ikeda T, Galli G, J. Phys. Chem. B, 101(8), 1332 (1997)
  9. Tsutsumi O, Kitsunai T, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(2), 355 (1998)
  10. Freiberg S, Lagugne-Labarthet F, Rochon P, Natansohn A, Macromolecules, 36(8), 2680 (2003)
  11. Cui L, Zhao Y, Yavrian A, Galstian T, Macromolecules, 36(22), 8246 (2003)
  12. Bo Q, Yavrian A, Galstian T, Zhao Y, Macromolecules, 38(8), 3079 (2005)
  13. Iftime G, Labarthet FL, Natansohn A, Rochon P, J. Am. Chem. Soc., 122(51), 12646 (2000)
  14. Andruzzi L, Altomare A, Ciardelli F, Solaro R, Hvilsted S, Ramanujam PS, Macromolecules, 32(2), 448 (1999)
  15. Liu J, Sun K, Li ZC, Gao JG, Su W, Yang J, Zhang JY, Wang P, Zhang QJ, Polymer, 45(12), 4331 (2004)
  16. Han M, Kidowaki M, Ichimura K, Ramanujam PS, Hvilsted S, Macromolecules, 34(12), 4256 (2001)
  17. Zebger I, Rutloh M, Hoffmann U, Stumpe J, Siesler HW, Hvilsted S, Macromolecules, 36(25), 9373 (2003)
  18. Anderle K, Wendorff JH, Mol. Cryst. Liq. Cryst., 243, 51 (1994)
  19. Han M, Ichimura K, Macromolecules, 34(1), 90 (2001)
  20. Craig AA, Winchester I, Madden PC, Larcey P, Hamley IW, Imrie CT, Polymer, 39(5), 1197 (1998)
  21. He XH, Zhang HL, Yan DY, Wang XY, J. Polym. Sci. A: Polym. Chem., 41(18), 2854 (2003)
  22. Chen JF, Zhang HL, Wang XZ, Wang XY, Polym. Bull., 53(4), 223 (2005)
  23. Abe J, Hasegawa M, Matsushima H, Shirai Y, Nemoto N, Nagase Y, Takamiya N, Macromolecules, 28(8), 2938 (1995)
  24. Dubois JC, Barney PL, Mauzac M, Noel C, 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 Ⅳ, p 207 (1998)
  25. Lee KS, Samoc M, Prasad PN, Comprehensive Polymer Science, First Supplement, S. L. Aggarwal and S. Russo, Editors, Pergamon Press, Oxford, Chap 16, p 407 (1992)
  26. Ichimura K, Chem. Rev., 100(5), 1847 (2000)
  27. Ikeda T, J. Mater. Chem., 13, 2037 (2003)
  28. Percec V, Pugh C, Side Chain Liquid Crystal Polymers, C. B. McArdle, Editor, Chapmann and Hall, New York, Chap 3, p 30 (1989)
  29. Simmonds DJ, Liquid Crystal Polymers: From Structures to Applications, A. A. Collyer, Editor, Elservier Applied Science, London and New York, Chap 7, p 349 (1992)
  30. Collings PJ, Hird M, Introduction to Liquid Crystals, G. W. Gray, J. W. Goodby, and A. Fukuda, Editors, Taylor and Francis Ltd., London, Chap 3, p 93 (1997)
  31. Jeong SY, Ma YD, Polym.(Korea), 30(1), 35 (2006)
  32. Jeong SY, Ma YD, Polym.(Korea), 31(4), 356 (2007)
  33. Jeong SY, Ma YD, Industrial Technology Research Paper(Dankook University), 8, 69 (2007)
  34. Jeong SY, Ma YD, Polym.(Korea), 31(1), 37 (2007)
  35. Jeong SY, Ma YD, J. Korean Ind. Eng. Chem., in press.
  36. Magagnini PL, Marchetti A, Matsa F, Pizzirani G, Turchi G, Eur. Polym. J., 10, 585 (1974)
  37. Baccaredda M, Magagnini PL, Pizziriani G, Giusti P, J. Polym. Sci. Polym. Lett., 9, 303 (1971)
  38. Bresci V, Frosini A, Lupinacci D, Magagnini PL, Macromol. Rapid Commun., 1, 183 (1980)
  39. Barny PL, Dubois JC, Friedrich C, Noel C, Polym. Bull., 15, 341 (1986)
  40. Le Barny P, Ravanx G, Dubois JC, Parneix JP, Njenmo R, Legrand C, Levelut AM, SPIE, 682, 56 (1986)
  41. Percec V, SPIE, Handbook of Liquid Crystal Research, P. J. Collings and J. S. Patel, Editors, Oxford University Press, Oxford, Chap 8, p 259, 682, 56 (1997)
  42. Percec V, Tomazos D, Comprehensive Polymer Science, First Supplement, S. L. AggarWal and S. Russo, Editors, Pergamon Press, Oxford, Chap 14, p 299 (1992)
  43. Fukuda T, Tsuji Y, Miyamoto T, Macromol. Symp., 99, 257 (1995)
  44. Jeong SY, Jeong JH, Ma YD, Tsujii Y, Polym.(Korea), 25(2), 279 (2001)
  45. Lam JWY, Kong XX, Dong YP, Cheuk KKL, Xu KT, Tang BZ, Macromolecules, 33(14), 5027 (2000)
  46. Gray GW, The Molecular Physics and Liquid Crystals, G. R. Luckhurst and G. W. Gray, Editors, Academic Press, New York, Chap 1, p 1 (1979)
  47. de Jeu WH, van der Veen J, Goossens WJA, Solid State Commun., 12, 405 (1979)
  48. Dowell F, Martire DE, J. Chem. Phys., 68, 1094 (1978)
  49. Craig AA, Imrie CT, Macromolecules, 28(10), 3617 (1995)
  50. Craig AA, Imrie CT, Macromolecules, 32(19), 6215 (1999)
  51. Yamaguchi T, Asada T, Hayashi H, Nakamura N, Macromolecules, 22, 1141 (1989)
  52. Maughon BR, Weck M, Mohr B, Grubbs RH, Macromolecules, 30(2), 257 (1997)
  53. Freidzon YS, Shibaev VP, Liquid-Crystal Polymers, N. A. Plate, Editor, Plenum Press, New York, Chap 7, p 251 (1993)
  54. Jeong SY, Ma YD, unpublished data
  55. Rodriguez-Parada J, Percec V, J. Polym. Sci. Chem. Ed, 24, 1363 (1986)
  56. Henderson PA, Cook AG, Imrie CT, Liq. Cryst., 31, 1427 (2004)
  57. Ciferri A, Liquid Crystallinity in Polymers, A. Ciferri, Editor, VCH Publisher, New York, Chap 6, p 209 (1991)
  58. Takada A, Fukuda T, Watanabe J, Miyamoto T, Macromolecules, 28(9), 3394 (1995)
  59. Imrie CT, Luckburst GR, Handbook of Liquid Crystals, D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, and V. Vill, Editors, Wiley-VCH, Weinheim-New York, Vol 2B, Chap Ⅹ, p 801 (1998)
  60. Chandrasekhar S, Liquid Crystals, Cambridge University Press, New York, Chap 2, p 17 (1992)
  61. 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, ChapⅠ, p 26 (1998)
  62. 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 Ι, p 52 (1998)
  63. Percec V, Asandei AD, Hill DH, Crawford D, Macromolecules, 32(8), 2597 (1999)
  64. Crag AA, Imrie CT, J. Mater. Chem., 4, 1705 (1994)
  65. Imrie CT, Karasz FE, Attard GS, Macromolecules, 26, 3803 (1993)
  66. Chen BQ, Kameyama A, Nishikubo T, Macromolecules, 32(20), 6485 (1999)