화학공학소재연구정보센터
Macromolecular Research, Vol.21, No.10, 1127-1137, October, 2013
Surface modification by self-assembled coating with amphiphilic comb-shaped block copolymers: A solution to the trade-off among solubility, adsorption and coating stability
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Surface coating with amphiphilic block copolymers containing a long hydrophobic anchor block in polar solvent often suffered from the damaging impact of micelles, often leading to a significant decrease in adsorption amount and packing density. In this study, a series of amphiphilic comb-shape block copolymers, poly[poly(ethylene glycol) methyl ether acrylate]-b-poly(styrene-co-N,N-dimethylacrylamide) (P(PEGMEA)-b-P(St-DMA)) were synthesized successfully by reversible addition-fragmentation chain transfer (RAFT) polymerization with fluorescencelabelled RAFT agent. The chain structure and chemical composition of copolymers were characterized by 1H NMR, FTIR and GPC. The surface self-assembled coating through physical adsorption of P(PEGMEA)-b-P(St-DMA) in ethanol on the surface of polyacrylonitrile (PAN) membrane was investigated by XPS, ATR-FTIR, SEM and water contact angle measurements. The antifouling properties of the modified membranes were evaluated using BSA as a model protein. It was found that the introduction of appropriate DMA (DMA/St in the range of about 0.1 to 0.2) into the hydrophobic segment can significantly increase the solubility of copolymers and alter their aggregation behaviors, alleviate the impact of micelles, increase adsorbed amount of copolymers, and thus can enhance the hydrophilicity and anti-fouling properties of membranes. Moreover, the stability analysis indicated that P(PEGMEA)-b-P(St-DMA) with appropriate DMA in the hydrophobic anchor block can form a relatively stable coating on the surface of PAN membrane. Consequently, the adjustment of the structure and composition of anchor segment may be a potential solution to the trade-off among solubility, adsorption amount and coating stability when amphiphilic block copolymers were used to surface modification by self-assembled coatings.
  1. Ulbricht M, Polymer, 47(7), 2217 (2006)
  2. Hwang TS, Park JW, Macromol. Res., 11(5), 347 (2003)
  3. Cha BJ, Yang JM, Macromol. Res., 14(6), 596 (2006)
  4. Nady N, Franssen MCR, Zuilhof H, Eldin MSM, Boom R, Schroen K, Desalination, 275(1-3), 1 (2011)
  5. Cho DL, Kim SH, Huh YI, Kim D, Cho SY, Kim BH, Macromol. Res., 12(6), 553 (2004)
  6. Susanto H, Arafat H, Janssen EML, Ulbricht M, Sep. Sci. Technol., 63, 558 (2008)
  7. Bernstein R, Anton E, Ulbricht M, ACS Appl. Mater. Interfaces, 4, 3438 (2012)
  8. Mu LJ, Zhao WZ, Appl. Surf. Sci., 255(16), 7273 (2009)
  9. Asatekin A, Menniti A, Kang ST, Elimelech M, Morgenroth E, Mayes AM, J. Membr. Sci., 285(1-2), 81 (2006)
  10. Fang BH, Ling QY, Zhao WF, Ma YL, Bai PL, Wei Q, Li HF, Zhao CS, J. Membr. Sci., 329(1-2), 46 (2009)
  11. Chiag YC, Chang Y, Chen WY, Ruaan RC, Langmuir, 28(2), 1399 (2012)
  12. Chang Y, Shih YJ, Ruaan RC, Higuchi A, Chen WY, Lai JY, J. Membr. Sci., 309(1-2), 165 (2008)
  13. Chang Y, Ko CY, Shih YJ, Quemener D, Deratani A, Wei TC, Wang DM, Lai JY, J. Membr. Sci., 345(1-2), 160 (2009)
  14. Ye SH, Watanabe J, Iwasaki Y, Ishihara K, J. Membr. Sci., 249(1-2), 133 (2005)
  15. Adout A, Kang S, Asatekin A, Mayes AM, Elimelech M, Environ. Sci. Technol., 44, 2406 (2010)
  16. Toomey R, Mays J, Yang JC, Tirrell M, Macromolecules, 39(6), 2262 (2006)
  17. Bijsterbosch HD, Stuart MAC, Fleer GJ, van Caeter P, Goethals EJ, Macromolecules, 31(21), 7436 (1998)
  18. Pagac ES, Prieve DC, Solomentsev Y, Tilton RD, Langmuir, 13(11), 2993 (1997)
  19. Kang YJ, Taton TA, Macromolecules, 38(14), 6115 (2005)
  20. Bijsterbosch HD, Stuart MAC, Fleer GJ, Macromolecules, 31(26), 9281 (1998)
  21. Dimitriou MD, Zhou ZL, Yoo HS, Killops KL, Finlay JA, Cone G, Sundaram HS, Lynd NA, Barteau KP, Campos LM, Fischer DA, Callow ME, Callow JA, Ober CK, Hawker CJ, Kramer EJ, Langmuir, 27(22), 13762 (2011)
  22. Su YL, Wang LJ, Yang XJ, Appl. Surf. Sci., 254(15), 4606 (2008)
  23. Revanur R, McCloskey B, Breitenkamp K, Freeman BD, Emrick T, Macromolecules, 40(10), 3624 (2007)
  24. Hyun J, Jang H, Kim K, Na K, Tak T, J. Membr. Sci., 282(1-2), 52 (2006)
  25. Popelka S, Machova L, Rypacek F, J. Colloid Interface Sci., 308(2), 291 (2007)
  26. Leermakers FAM, Gast AP, Macromolecules, 24, 718 (1991)
  27. Mansura CRE, Spinellia LS, Lucasa EF, Gonzalezb G, Colloids Surf. A: Physicochem. Eng. Asp., 149, 291 (1999)
  28. Nam YS, Kang HS, Par JYk, Park TG, Han SH, Chang IS, Biomaterials, 24, 2053 (2003)
  29. Zhang JH, Dong AJ, Cao TY, Guo RW, Eur. Polym. J., 44, 1071 (2008)
  30. Guo RW, Wang XX, Guo CG, Dong AJ, Zhang JH, Macromol. Chem. Phys., 213, 1851 (2012)
  31. Zhang JH, Guo RW, Qi GC, Liu M, Dong AJ, Acta Polym. Sin., 6, 691 (2010)
  32. Zhou D, Zhu XL, Zhu J, Cheng ZP, J. Polym. Sci. A: Polym. Chem., 46(18), 6198 (2008)
  33. Munch MR, Gast AP, J. Chem. Soc.-Faraday Trans., 86, 1341 (1990)
  34. Chaduc I, Zhang WJ, Rieger J, Lansalot M, D'Agosto F, Charleux B, Macromol. Rapid Commun., 32(16), 1270 (2011)
  35. Strube O, Nothdurft L, Abisheva Z, Schmidt-Naake G, Macromol. Chem. Phys., 213, 1274 (2012)
  36. Mertoglu M, Garnier S, Laschewsky A, Skrabania K, Storsberg J, Polymer, 46(18), 7726 (2005)
  37. Guo RW, Shi ZP, Wang XX, Dong AJ, Zhang JH, Polym. Chem., 3, 1314 (2012)
  38. Rieger J, Zhang WJ, Stoffelbach F, Charleux B, Macromolecules, 43(15), 6302 (2010)
  39. Elmiloudi K, Djadoun S, Macromol. Symp., 265, 89 (2008)
  40. Nichifor M, Zhu XX, Polymer, 44(10), 3053 (2003)
  41. Park SY, Han BR, Na KM, Han DK, Kim SC, Macromolecules, 36(11), 4115 (2003)
  42. Kingshott P, Thissen H, Griesser HJ, Biomaterials, 23, 2043 (2002)
  43. Fleer GJ, Cohen-Stuart MA, Scheutjens JMHM, Cosgrove T, Vincent B, Polymers at Interfaces, Chapman and Hall, London, 1993.
  44. Meiners JC, Quintelritzi A, Mlynek J, Elbs H, Krausch G, Macromolecules, 30(17), 4945 (1997)
  45. Chen XR, Su Y, Shen F, Wan YH, J. Membr. Sci., 384(1-2), 44 (2011)
  46. Henrici-Olive G, Olive S, Adv. Polym. Sci., 32, 123 (1979)
  47. Henrici-Olive G, Olive S, Adv. Polym. Sci., 51, 1 (1983)
  48. Feichtmayr F, Wurz A, J. Soc. Dyers Colour., 77, 626 (1961)
  49. Wyszogrodzka M, Haag R, Biomacromolecules, 10(5), 1043 (2009)
  50. Chang Y, Chen SF, Zhang Z, Jiang SY, Langmuir, 22(5), 2222 (2006)
  51. Zhu LP, Xu L, Zhu BK, Feng YX, Xu YY, J. Membr. Sci., 294(1-2), 196 (2007)
  52. Henis JMS, Tripodi MK, J. Membr. Sci., 8, 233 (1981)
  53. Ji PF, Cao YM, Zhao HY, Kang GD, Jie XM, Liu DD, Liu JH, Yuan Q, J. Membr. Sci., 342(1-2), 190 (2009)