Skip to main content
SpringerLink
Log in

Synthesis of pH-responsive amphiphilic diblock copolymers containing polyisobutylene via oxyanion-initiated polymerization and their multiple self-assembly morphologies

  • Paper
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-(N,N-dimethylamino) ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA), were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-olefin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O−K+). PIB-O−K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography (GPC). These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Gil, E.S. and Hudson, S.M., Prog. Polym. Sci., 2004, 29: 1173

    Article  CAS  Google Scholar 

  2. Liu, F. and Urban, M.W., Prog. Polym. Sci., 2010, 35: 3

    Article  CAS  Google Scholar 

  3. Roy, D., Cambre, J.N. and Sumerlin, B.S., Prog. Polym. Sci., 2010, 35: 278

    Article  CAS  Google Scholar 

  4. Percec, V., Wilson, D.A., Leowanawat, P., Wilson, C.J., Hughes, A.D., Kaucher, M.S., Hammer, D.A., Levine, D.H., Kim, A.J., Bates, F.S., Davis, K.P., Lodge, T.P., Klein, M.L., DeVane, R.H., Aqad, E., Rosen, B.M., Argintaru, A.O., Sienkowska, M.J., Rissanen, K., Nummelin, S. and Ropponen, J., Science, 2010, 328: 1009

    Article  CAS  Google Scholar 

  5. Percec, V., Imam, M.R., Peterca, M. and Leowanawat, P., J. Am. Chem. Soc., 2012, 134: 4408

    Article  CAS  Google Scholar 

  6. Jain, S. and Bates, F.S., Science, 2003, 300: 460

    Article  CAS  Google Scholar 

  7. Discher, B.M., Won, Y.Y., Ege, D.S., Lee, J.C.M., Bates, F.S., Discher, D.E. and Hammer, D.A., Science, 1999, 284: 1143

    Article  CAS  Google Scholar 

  8. Pochan, D.J., Chen, Z.Y., Cui, H.G., Hales, K., Qi, K. and Wooley, K.L., Science, 2004, 306: 94

    Article  CAS  Google Scholar 

  9. Zhang, L.F. and Eisenberg, A., J. Am. Chem. Soc., 1996, 118: 3168

    Article  CAS  Google Scholar 

  10. Soo, P.L. and Eisenberg, A., J. Polym. Sci. Part B: Polym. Phys., 2004, 42: 923

    Article  CAS  Google Scholar 

  11. Zhang, W.L., He, J.L., Liu, Z., Ni, P.H. and Zhu, X.L., J. Polym. Sci. Part A: Polym. Chem., 2011, 48: 1079

    Article  Google Scholar 

  12. Dai, S., Ravi, P. and Tam, K.C., Soft Matter, 2008, 4: 435

    Article  CAS  Google Scholar 

  13. Pilon, L.N., Armes, S.P., Findlay, P. and Rannard, S.P., Langmuir, 2005, 21: 3808

    Article  CAS  Google Scholar 

  14. Zhang, Y.W., Jiang, M., Zhao, J.X., Wang, Z.X., Dou, H.J. and Chen, D.Y., Langmuir, 2005, 21: 1531

    Article  CAS  Google Scholar 

  15. Tanner, P., Baumann, P., Enea, R., Onaca, O., Palivan, C. and Meier, W., Acc. Chem. Res., 2011, 44: 1039

    Article  CAS  Google Scholar 

  16. Riess, G., Prog. Polym. Sci., 2003, 28: 1107

    Article  CAS  Google Scholar 

  17. Blanazs, A., Armes, S.P. and Ryan, A.J., Macromol. Rapid Commun., 2009, 30: 267

    Article  CAS  Google Scholar 

  18. Zhao, Y., Luo, Y.W., Li, B.G. and Zhu, S.P., Langmuir, 2011, 27: 11306

    Article  CAS  Google Scholar 

  19. Li, Y., Wu, Y.X., Liang, L.H., Li, Y. and Wu, G.Y., Chinese J. Polym. Sci., 2010, 28(1): 55

    Article  CAS  Google Scholar 

  20. Liang, L.H., Wu, G.Y., Li, Y., Xu, R.W., Yang, W.T. and Wu, G.Y., Acta Polymerica Sinica (in Chinese), 2008, (12): 1166

    Google Scholar 

  21. Pinchuk, L., Wilson, G.J., Barry, J.J., Schoephoerster, R.T., Parel, J.M. and Kennedy, J.P., Biomaterials, 2008, 29: 448

    Article  CAS  Google Scholar 

  22. Sipos, L., Som, A. and Faust, R., Biomacromolecules, 2005, 6: 2570

    Article  CAS  Google Scholar 

  23. Kaszas, G., Puskas, J.E., Kennedy, J.P. and Hager, W.G., J. Polym. Sci. Part A: Polym. Chem., 1991, 29: 427

    Article  CAS  Google Scholar 

  24. Ranade, S.V., Miller, K.M., Richard, R.E., Chan, A.K., Allen, M.J. and Helmus, M.N., J. Biomed. Mater. Res., 2004, 71A: 625

    Article  CAS  Google Scholar 

  25. Fray, M.E., Prowans, P., Puskas, J.E. and Altstädt, V., Biomacromolecules, 2006, 7: 844

    Article  Google Scholar 

  26. Jewrajka, S.K., Yilgor, E., Yilgor, I. and Kennedy, J.P., J. Polym. Sci. Part A: Polym. Chem., 2009, 47: 38

    Article  CAS  Google Scholar 

  27. Jewrajka, S.K., Kang, J.M., Erdodi, G., Kennedy, J.P., Yilgor, E. and Yilgor, I., J. Polym. Sci. Part A: Polym. Chem., 2009, 47: 2787

    Article  CAS  Google Scholar 

  28. Kwon, Y.H., Faust, R., Chen, C.X. and Thomas, E.L., Macromolecules, 2002, 35: 3348

    Article  CAS  Google Scholar 

  29. Martinez-Castro, N., Lanzendörfer, M.G., Müller, A.H.E., Cho, J.C., Acar, M.H. and Faust, R., Macromolecules, 2003, 36: 6985

    Article  CAS  Google Scholar 

  30. Feng, D.S., Chandekar, A., Whitten, J.E. and Faust, R., ACS Div. Polym. Chem. Polym. Prepr., 2007, 48: 1017

    CAS  Google Scholar 

  31. Cho, J.C., Cheng, G.L., Feng, D.S., Faust, R., Richard, R., Schwarz, M., Chan, K. and Boden, M., Biomacromolecules, 2006, 7: 2997

    Article  CAS  Google Scholar 

  32. Higashihara, T., Feng, D.S. and Faust, R., Macromolecules, 2006, 39: 5275

    Article  CAS  Google Scholar 

  33. Binder, W.H., Kurzhals, S., Pulamagatta, B., Decker, U., Pawar, G.M., Wang, D.R., Kühnel, C. and Buchmeiser, M.R., Macromolecules, 2008, 41: 8405

    Article  CAS  Google Scholar 

  34. Fang, Z. and Kennedy, J.P., J. Polym. Sci. Part A: Polym. Chem., 2002, 40: 3662

    Article  CAS  Google Scholar 

  35. Storey, R.F., Scheuer, A.D., Achord, B.C. and Brandon, C., J. Macromol. Sci. Part A: Pure. Appl. Chem., 2006, 43: 1493

    Article  CAS  Google Scholar 

  36. Breland, L.K., Murphy, J.C. and Storey, R.F., Polymer, 2006, 47: 1852

    Article  CAS  Google Scholar 

  37. Jakubowski, W., Tsarevsky, N.V., Higashihara, T., Faust, R. and Matyjaszewski, K., Macromolecules, 2008, 41: 2318

    Article  CAS  Google Scholar 

  38. Breland, L.K. and Storey, R.F., Polymer, 2008, 49: 1154

    Article  CAS  Google Scholar 

  39. Zhu, Y.L. and Storey, R. F., Macromolecules, 2010, 43: 7048

    Article  CAS  Google Scholar 

  40. Magenau, A.J.D., Martinez-Castro, N. and Storey, R.F., Macromolecules, 2009, 42: 2353

    Article  CAS  Google Scholar 

  41. Magenau, A.J.D., Martinez-Castro, N., Savin, D.A. and Storey, R.F., Macromolecules, 2009, 42: 8044

    Article  CAS  Google Scholar 

  42. Magenau, A.J.D., Hartlage, T.R. and Storey, R.F., J. Polym. Sci. Part A: Polym. Chem., 2010, 48: 5505

    Article  CAS  Google Scholar 

  43. Martinez-Castro, N., Magenau, A.J.D. and Storey, R.F., J. Polym. Sci. Part A: Polym. Chem., 2010, 48: 2533

    Article  CAS  Google Scholar 

  44. Schunack, M., Gragert, M., Döhler, D., Michael, P. and Binder, W.H., Macromol. Chem. Phys., 2012, 213: 205

    Article  CAS  Google Scholar 

  45. Binder, W.H. and Machl, D., J. Polym. Sci. Part A: Polym. Chem., 2005, 43: 188

    Article  CAS  Google Scholar 

  46. Puskas, J.E., Dos Santos, L.M., Kaszas, G. and Kulbaba, K., J. Polym. Sci. Part A: Polym. Chem., 2009, 47: 1148

    Article  CAS  Google Scholar 

  47. Binder, W.H., Kunz, M.J. and Ingolic, E. J. Polym. Sci. Part A: Polym. Chem., 2004, 42: 162

    Article  CAS  Google Scholar 

  48. Binder, W.H., Kunz, M.J., Kluger, C., Hayn, G. and Saf, R., Macromolecules, 2004, 37: 1749

    Article  CAS  Google Scholar 

  49. Binder, W.H., Bernstroff, S., Kluger, C., Petraru, L. and Kunz, M.J., Adv. Mater., 2005, 17: 2824

    Article  CAS  Google Scholar 

  50. Tomoi, M., Sekiya, K. and Kakiuchi, H., Polym. J., 1974, 6: 438

    Article  CAS  Google Scholar 

  51. Iijima, M., Nagasaki, Y., Kato, M. and Kataoka, K., Polymer, 1997, 38: 1197

    Article  Google Scholar 

  52. Vamvakaki, M., Billingham, N.C. and Armes, S.P., Macromolecules, 1999, 32: 2088

    Article  CAS  Google Scholar 

  53. Liu, Q.Q. and Ni, P.H., Chemistry (in Chinese), 2003, 66(12): w118

    Google Scholar 

  54. Zhao, Q. and Ni, P.H., Polymer, 2005, 46: 3141

    Article  CAS  Google Scholar 

  55. Mao, J., Ni, P.H., Mai, Y.Y. and Yan, D.Y., Langmuir, 2007, 23: 5127

    Article  CAS  Google Scholar 

  56. Zhang, H., Ni, P.H., He, J.L. and Liu, C.C., Langmuir, 2008, 24: 4647

    Article  CAS  Google Scholar 

  57. He, J.L., Ni, P.H. and Liu, C.C., J. Polym. Sci. Part A: Polym. Chem., 2008, 46: 3029

    Article  CAS  Google Scholar 

  58. Gu, Z.X., Yuan, Y., He, J.L., Zhang, M.Z. and Ni, P.H., Langmuir, 2009, 25: 5199

    Article  CAS  Google Scholar 

  59. Zhang, S.H., Gu, Z.X., Hao, Y., Zhang, M.Z. and Ni, P.H., J. Polym. Sci. Part A: Polym. Chem., 2011, 49: 4081

    Article  CAS  Google Scholar 

  60. Hao, Y., Zhang, M.Z., He, J.L. and Ni, P.H., Langmuir, 2012, 28: 6448

    Article  CAS  Google Scholar 

  61. Vasilenko, I.V., Frolov, A.N. and Kostjuk, S.V., Macromolecules, 2010, 43: 5503

    Article  CAS  Google Scholar 

  62. Morgan, D.L., Harrison, J.J., Stokes, C.D. and Storey, R.F., Macromolecules, 2011, 44: 2438

    Article  CAS  Google Scholar 

  63. Zhang, C.L., Wu, Y.X., Meng, X.Y., Huang, Q.G., Wu, G.Y. and Xu, R.W., Chinese J. Polym. Sci., 2009, 27(4): 551

    Article  CAS  Google Scholar 

  64. Lin, T., Wu, Y.X., Ye, X.L., Zhang, L.B., Huang, Q.G. and Wu, G.Y., Acta Polymerica Sinica (in Chinese), 2008, (2): 129

    Article  Google Scholar 

  65. Zhang, L.F. and Eisenberg, A., J. Polym. Sci. Part B: Polym. Phys., 1999, 37: 1469

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Soochow University, Suzhou, 215123, China

    Huai-chao Wang, Ming-zu Zhang, Pei-hong Ni  (倪沛红), Jin-lin He & Ying Hao

  2. State Key Lab of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Yi-xian Wu

Authors
  1. Huai-chao Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ming-zu Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pei-hong Ni  (倪沛红)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jin-lin He
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ying Hao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yi-xian Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Pei-hong Ni  (倪沛红).

Additional information

The work was financially supported by the National Natural Science Foundation of China (Nos. 20974074 and 21074078), Natural Science Foundation of Jiangsu Province for Rolling Support Project (BK2011045), a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions, State Key Lab of Chemical Resource Engineering (Beijing University of Chemical Technology), the Innovation Project of Graduate Students of Jiangsu Province, China (CXZZ11_0091).

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wang, Hc., Zhang, Mz., Ni, Ph. et al. Synthesis of pH-responsive amphiphilic diblock copolymers containing polyisobutylene via oxyanion-initiated polymerization and their multiple self-assembly morphologies. Chin J Polym Sci 31, 218–231 (2013). https://doi.org/10.1007/s10118-013-1208-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-013-1208-9

Keywords

Search

Navigation