화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.18, No.3, 271-278, March, 2010
DOI10.1007/s13233-010-0311-9  Export Citation
Nanocomposite proton conducting membranes based on amphiphilic PVDF graft copolymer
Dong Kyu Roh, Jin Kyu Choi, Jong Kwan Koh, Yong Gun Shul, and Jong Hak Kim†
  • Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, 120-749, Korea
E-mail:
A novel comb-like amphiphilic graft copolymer of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(4-styrene sulfonic acid-co-trimethoxysilyl propyl methacrylate), i.e. P(VDF-co-CTFE)-g-P(SSA-co-TMSPMA) was synthesized using an atom transfer radical polymerization (ATRP) technique. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (H-1 NMR), FTIR spectroscopy and transmission electron microscopy (TEM). This graft copolymer was combined with tetraethoxysilane (TEOS) under acidic conditions to produce organic-inorganic nanocomposite membranes through an in-situ sol-gel reaction between TEOS and PTMSPMA, as characterized by X-ray diffraction (XRD) and TEM. Upon the introduction of silica, the proton conductivity and water uptake of the membranes decreased slightly but the thermal and mechanical properties of the membranes were enhanced significantly. Various morphologies of the nanocomposite membranes were obtained after controlling the TEOS concentration, which were correlated with the thermal, mechanical and transport properties.
Keywords:atom transfer radical polymerization (ATRP);graft copolymer;nanocomposite;sol-gel;polymer electrolyte membrane
  1. Harris DJ, Bonagamba TJ, Schmidt-Rohr K, Soo PP, Sadoway DR, Mayes AM, Macromolecules, 73, 3772 (2002)
  2. Chiu CY, Hsu WH, Yen YJ, Kuo SW, Chang FC, Macromolecules, 38(15), 6640 (2005)
  3. Kim JH, Kang MS, Kim YJ, Won J, Park NG, Kang YS, Chem. Commun., 1662 (2004)
  4. Stergiopoulos T, Arabatzis IM, Katsaros G, Falaras P, Nano Lett., 2, 1259 (2002)
  5. Fungo F, Jenekhe SA, Bard AJ, Chem. Mater., 15, 1264 (2003)
  6. Kim JH, Min BR, Won J, Joo SH, Kim HS, Kang YS, Macromolecules, 36(16), 6183 (2003)
  7. Daletou MK, Kallitsis JK, Voyiatzis G, Neophytides SG, J. Membr. Sci., 326(1), 76 (2009)
  8. Lee DK, Park JT, Roh DK, Min BR, Kim JH, Macromol. Res., 17(5), 325 (2009)
  9. Reiter J, Velicka J, Mika M, Electrochim. Acta, 53(26), 7769 (2008)
  10. Mikhailenko SUD, Wang KP, Kaliaguine S, Xing PX, Robertson GP, Guiver MD, J. Membr. Sci., 233(1-2), 93 (2004)
  11. Kim DS, Robertson GP, Guiver MD, Lee YM, J. Membr. Sci., 281(1-2), 111 (2006)
  12. Li J, Lee CH, Park HB, Lee YM, Macromol. Res., 14(4), 438 (2006)
  13. Kim DS, Guiver MD, Seo MY, Cho HI, Kim DH, Rhim JW, Moon GY, Nam SY, Macromol. Res., 15(5), 412 (2007)
  14. Shen M, Roy S, Kuhlmann JW, Scott K, Lovell K, Horsfall JA, J. Membr. Sci., 251(1-2), 121 (2005)
  15. Nasef MM, Zubir NA, Ismail AF, Khayet M, Dahlan KZM, Saidi H, Rohani R, Ngah TIS, Sulaiman NA, J. Membr. Sci., 268(1), 96 (2006)
  16. Holmberg S, Holmlund P, Nicolas R, Wilen CE, Kallio T, Sundholm G, Sundholm F, Macromolecules, 37(26), 9909 (2004)
  17. Holmberg S, Holmlund P, Wilen CE, Kallio T, Sundholm G, Sundholm F, J. Polym. Sci. A: Polym. Chem., 40(4), 591 (2002)
  18. Shen Y, Qiu XP, Shen J, Xi JY, Zhu WT, J. Power Sources, 161(1), 54 (2006)
  19. Liu DM, Chen YW, Zhang N, He XH, J. Appl. Polym. Sci., 101(6), 3704 (2006)
  20. Chen Y, Liu D, Mang N, Surf. Rev. Lett., 12, 709 (2005)
  21. Kim YW, Choi JK, Park JT, Kim JH, J. Membr. Sci., 313(1-2), 315 (2008)
  22. Kim YW, Park JT, Koh JH, Roh DK, Kim JH, J. Membr. Sci., 325(1), 319 (2008)
  23. Di Vona ML, Ahmed Z, Bellitto S, Lenci A, Traversa E, Licoccia S, J. Membr. Sci., 296(1-2), 156 (2007)
  24. Licoccia S, Di Vona ML, D'Epifanio A, Ahmed Z, Bellitto S, Marani D, Mecheri B, de Bonis C, Trombetta M, Traversa E, J. Power Sources, 167(1), 79 (2007)
  25. Tang H, Wan Z, Pan M, Jiang SP, Electrochem. Commun., 9, 2003 (2007)
  26. Ramani V, Kunz HR, Fenton JM, J. Membr. Sci., 266(1-2), 110 (2005)
  27. Ramani V, Kunz HR, Fenton JM, J. Power Sources, 152(1), 182 (2005)
  28. Sambandam S, Ramani V, J. Power Sources, 170(2), 259 (2007)
  29. Tang HL, Pan M, J. Phys. Chem., 112, 11556 (2008)
  30. Ladewig BP, Knott RB, Hill AJ, Riches JD, White JW, Martin DJ, da Costa JCD, Lu GQ, Chem. Mater., 19, 2372 (2007)
  31. Zhang MF, Russell TP, Macromolecules, 39(10), 3531 (2006)
  32. Hester JF, Banerjee P, Won YY, Akthakul A, Acar MH, Mayes AM, Macromolecules, 35(20), 7652 (2002)
  33. Okamura H, Takatori Y, Tsunooka M, Shirai M, Polymer, 43(11), 3155 (2002)
  34. Zhou J, Wang L, Dong X, Yang Q, Wang J, Yu H, Chen X, Eur. Polym. J., 43, 1736 (2007)
  35. Chen CC, Lin DJ, Don TM, Huang FH, Cheng LP, J. Non-Cryst. Solids, 354, 3828 (2008)
  36. Lu SR, Zhang HL, Zhao CX, Wang XY, J. Appl. Polym. Sci., 101(2), 1075 (2006)
  37. Ji X, Eric HJ, Hu Q, He J, Yang Z, Lu Y, Chem. Mater., 15, 3656 (2003)
  38. Yoon S, Prabu AA, Kim KJ, Park C, Macromol. Rapid Commun., 29(15), 1316 (2008)
  39. Mokrini A, Acosta JL, Polymer, 42(1), 9 (2001)
  40. Tang HL, Pan M, J. Phys. Chem., 112, 11556 (2008)
  41. Hagihara H, Uchida H, Watanabe M, Electrochim. Acta, 51(19), 3979 (2006)
  42. Ramachandra P, Ramani R, Ravichandran TS, Ramgopal G, Gopal S, Ranganathaiah C, Murthy NS, Polymer, 37(15), 3233 (1996)
  43. Kim B, Jung B, Macromol. Rapid Commun., 25(13), 1263 (2004)
  44. Ladewig BP, Knott RB, Hill AJ, Riches JD, White JW, Martin DJ, da Costa JCD, Lu GQ, Chem. Mater., 19, 2372 (2007)
  45. Bandyopadhyay A, De Sarkar M, Bhowmick A, J. Mater. Sci., 40(19), 5233 (2005)