화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.29, No.7, 470-476, July, 2021
DOI10.1007/s13233-021-9061-0  Export Citation
Well-Defined ABA Triblock Copolymers Containing Carbazole and Ethynyl Groups: Living Anionic Polymerization, Postpolymerization Modification, and Thermal Cross-Linking
Beom-Goo Kang†
  • Department of Chemical Engineering, Soongsil University, Seoul 06978, Korea
E-mail:
A block copolymer that can be thermally cross-linked is synthesized by copolymerization of N-phenyl-2-vinylcarbazole (A) and trimethyl(2-(4-vinylphenyl) ethynyl)silane (B), followed by a deprotection reaction (d-PBAB). A t riblock copolymer containing carbazole and (trimethylsilyl)ethynyl groups (PBAB) is first prepared using potassium naphthalenide in tetrahyrdofuran at -78℃for 60 min. Well-controlled poly(A) and PBAB can be obtained under the conditions employed in this anionic block copolymerization. The well-defined d-PBAB with thermally cross-linkable ethynyl group is then prepared by the deprotection of the trimethylsilyl group from PBAB without side reactions. The thermal cross-linking behavior of d-PBAB is investigated using thermogravimetric analysis and differential scanning calorimetry. The d-PBAB is cross-linked under different conditions, and it is observed that the d-PBAB film heated at 250℃for 60 min shows excellent solvent resistance and increased film density. In addition, the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of cross-linked d-PBAB are estimated to be -5.09 and -1.57 eV, respectively.
Keywords:anionic polymerization;block copolymer;carbazole group;ethynyl group;deprotection;thermal cross-linking
  1. Hirao A, Loykulnant S, Ishizone T, Progr. Polym. Sci., 70, 1399 (2002)
  2. Ahn JH, Shin YD, Nath GY, Park SY, Rahman MS, Samal S, Lee JS, J. Am. Chem. Soc., 127(12), 4132 (2005)
  3. Uhrig D, Mays JW, J. Polym. Sci. A: Polym. Chem., 43(24), 6179 (2005)
  4. Kang BG, Kang NG, Lee JS, Macromolecules, 43(20), 8400 (2010)
  5. Hirao A, Goseki R, Ishizone T, Macromolecules, 47(6), 1883 (2014)
  6. Hirao A, Hadjichristidis N, Anionic Polymerization: Principles, Practice, Strength, Consequences and Applications, Springer, Tokyo, 2015.
  7. Li J, He J, ACS Marcro Lett., 4, 372 (2015)
  8. Otake K, Matsumoto M, Tanaka S, Uchida S, Goseki R, Hirao A, Ishizone T, Macromol. Chem. Phys., 218, 160055 (2017)
  9. Polymeropoulos G, Zapsas G, Ntetsikas K, Bilalis P, Gnanou Y, Hadjichristidis N, Macromolecules, 50(4), 1253 (2017)
  10. Kobayashi S, Kataoka H, Goseki R, Ishizone T, Macromol. Chem. Phys., 219, 170045 (2018)
  11. Hirao A, Tsunoda Y, Matsuo A, Sugiyama K, Watanabe T, Macromol. Res., 14(3), 272 (2006)
  12. Higashihara T, Inoue K, Nagura M, Hirao A, Macromol. Res., 14(3), 287 (2006)
  13. Cho YS, Kim SW, Ihn CS, Lee JS, Polymer, 42(18), 7611 (2001)
  14. Cho YS, Lee JS, Cho GJ, Polymer, 43(4), 1197 (2002)
  15. Natori I, Macromolecules, 39(18), 6017 (2006)
  16. Kang BG, Kang NG, Lee JS, J. Polym. Sci. A: Polym. Chem., 49(24), 5199 (2011)
  17. Kang BG, Yu YG, Kang NG, Lee JS, J. Polym. Sci. A: Polym. Chem., 51(19), 4233 (2013)
  18. Kang BG, Song S, Cho B, Kang NG, Kim MJ, Lee T, Lee JS, J. Polym. Sci. A: Polym. Chem., 52(18), 2625 (2014)
  19. Kang NG, Hur YH, Changez M, Kang BG, Yu YG, Lee JS, Polymer, 54(21), 5615 (2013)
  20. Ledwon P, Org. Electron., 75, 105422 (2019)
  21. Hudson ZM, Wang ZB, Helander MG, Lu ZH, Wang SN, Adv. Mater., 24(21), 2922 (2012)
  22. Song M, Park JS, Yoon M, Yoon HW, Kim AJ, Jin SH, Gal YS, Lee JH, Lee JW, Macromol. Res., 18(11), 1088 (2010)
  23. Li J, Grimsdale AC, Chem. Soc. Rev., 39, 2399 (2010)
  24. Liu F, Wu F, Ling W, Tu Z, Zhang J, Wei Z, Zhu L, Li Q, Li Z, ACS Energy Lett., 4, 2514 (2019)
  25. Baek MJ, Lee SH, Kim DH, Lee YS, Macromol. Res., 20(2), 147 (2012)
  26. Kang NG, Cho B, Kang BG, Song S, Lee T, Lee JS, Adv. Mater., 24(3), 385 (2012)
  27. Hahm SG, Kang NG, Kwon W, Kim K, Ko YG, Ahn S, Kang BG, Chang T, Lee JS, Ree M, Adv. Mater., 24(8), 1062 (2012)
  28. Wi D, Kim J, Lee H, Kang NG, Lee J, Kim MJ, Lee JS, Ree M, J. Mater. Chem. C, 4, 2017 (2016)
  29. Tsuda K, Hirahata W, Yokota K, Kakuchi T, Ishizone T, Hirao A, Polym. Bull, 39, 173 (1997)
  30. Kim JP, Lee WY, Kang JW, Kwon SK, Kim JJ, Lee JS, Macromolecules, 34(22), 7817 (2001)
  31. Lee KS, Jeong MH, Lee JP, Lee JS, Macromolecules, 42(3), 584 (2009)
  32. Jeong MH, Lee KS, Lee JS, J. Membr. Sci., 337(1-2), 145 (2009)
  33. Kang BG, Kang H, Kang NG, Lee CL, Lee K, Lee JS, Polym. Chem, 4, 969 (2013)
  34. Kang BG, Jang J, Song Y, Kim MJ, Lee T, Lee JS, Polym. Chem, 6, 4264 (2015)
  35. Vanherck K, Koeckelberghs G, Vankelecom IF, Progr. Polym. Sci., 38, 874 (2013)
  36. Ishizone T, Hirao A, Nakahama S, Kakuchi T, Yokota K, Tsuda K, Macromolecules, 24, 5230 (1991)
  37. Tsuda K, IsIhizone T, Hirao A, Nakahama S, Kakuchi T, Yokota K, Macromolecules, 26, 6985 (1993)
  38. Qin AJ, Jim CKW, Lu WX, Lam JWY, Haussler M, Dong YQ, Sung HHY, Williams ID, Wong GKL, Tang BZ, Macromolecules, 40(7), 2308 (2007)
  39. Yao ZK, Yu ZX, J. Am. Chem. Soc., 133(28), 10864 (2011)
  40. Sun W, Deng Y, Jin Y, Guo X, Zhang Q, ACS Appl. Polym. Mater., 2, 3274 (2020)
  41. Ahn SK, Ban T, Sakthivel P, Jin SH, Gal YS, Lee JH, Macromol. Res., 20(5), 459 (2012)
  42. Hong H, Jo MY, Ha YE, Kim JH, Macromol. Res., 21(3), 321 (2013)
  43. Jiang XZ, Liu S, Liu MS, Herguth P, Jen AKY, Sarikaya M, Adv. Funct. Mater., 12(11-12), 745 (2002)
  44. Su WF, Chen RT, Chen Y, J. Polym. Sci. A: Polym. Chem., 49(2), 352 (2011)
  45. Lei Y, Niu Q, Mi H, Wang Y, Nurulla I, Shi W, Dyes Pigment., 96, 138 (2013)
  46. Kuorosawa T, Chueh CC, Liu CL, Higashihara T, Ueda M, Chen WC, Macromolecules, 43(3), 1236 (2010)
  47. Hsu JC, Chen YG, Kakuchi T, Chen WC, Macromolecules, 44(13), 5168 (2011)
  48. Lee JY, Yun CY, Reddy MR, Ho GD, Kim CI, Seo SY, Macromol. Res., 28(7), 654 (2020)