Anionic synthesis of a “clickable” middle-chain azidefunctionalized polystyrene and its application in shape amphiphiles

Abstract

“Click chemistry” is, by definition, a general functionalization methodology (GFM) and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis. This paper reports the synthesis of a “clickable” middle-chain azide-functionalized polystyrene (mPS-N3) by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane (POSS). The mPS-N3 was synthesized by coupling living poly(styryl)lithium chains (PSLi) with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide. Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography. The mPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential “click” strategy. The copper(I)-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative (VPOSS-alkyne) ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain (mPS-VPOSS). The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls, resulting in an amphiphilic shape amphiphile, mPS-DPOSS. This synthetic approach is highly efficient and modular. It demonstrates the “click” philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile “clickable” motif in polymer science for the precise synthesis of complex macromolecules.

This is a preview of subscription content, access via your institution.

References

  1. 1

    Hsieh, H.L. and Quirk, R.P., “Anionic polymerization: principles and practical applications”, Marcel Dekker, New York, 1996

    Google Scholar 

  2. 2

    Baskaran, D. and Muller, A.H.E., Prog. Polym. Sci., 2007, 32: 173

    Article  CAS  Google Scholar 

  3. 3

    Hadjichristidis, N., Pitsikalis, M., Pispas, S. and Iatrou, H., Chem. Rev., 2001, 101: 3747

    Article  CAS  Google Scholar 

  4. 4

    Quirk, R.P., Yoo, T., Lee, Y., Kim, J. and Lee, B., Adv. Polym. Sci., 2000, 153: 67

    Article  CAS  Google Scholar 

  5. 5

    Tasdelen, M.A., Kahveci, M.U. and Yagci, Y., Prog. Polym. Sci., 2011, 36: 455

    Article  CAS  Google Scholar 

  6. 6

    Quirk, R.P., Mathers, R.T., Ma, J.J., Wesdemiotis, C. and Arnould, M.A., Macromol. Symp., 2002, 183: 17

    Article  CAS  Google Scholar 

  7. 7

    Quirk, R.P. and Ma, J.J., J. Polym. Sci., Part A: Polym. Chem., 1988, 26: 2031

    Article  CAS  Google Scholar 

  8. 8

    Quirk, R.P., Kim, H., Polce, M.J. and Wesdemiotis, C., Macromolecules, 2005, 38: 7895

    Article  CAS  Google Scholar 

  9. 9

    Bellas, V. and Rehahn, M., Macromol. Rapid Commun., 2007, 28: 1415

    Article  CAS  Google Scholar 

  10. 10

    Quirk, R.P., Janoski, J., Chowdhury, S.R., Wesdemiotis, C. and Dabney, D.E., Macromolecules, 2009, 42: 494

    Article  CAS  Google Scholar 

  11. 11

    Zhang, W.B., Sun, B., Li, H., Ren, X., Janoski, J., Sahoo, S., Dabney, D.E., Wesdemiotis, C., Quirk, R.P. and Cheng, S.Z.D., Macromolecules, 2009, 42: 7258

    Article  CAS  Google Scholar 

  12. 12

    Li, Y.W., Zhang, W.B., Janoski, J.E., Li, X.P., Dong, X.H., Wesdemiotis, C., Quirk, R.P. and Cheng, S.Z.D., Macromolecules, 2011, 44: 3328

    Article  CAS  Google Scholar 

  13. 13

    Quirk, R.P., Janoski, J., Chowdhury, S.R., Wesdemiotis, C. and Dabney, D.E., Macromolecules, 2008, 42: 494

    Article  Google Scholar 

  14. 14

    Yu, X., Zhong, S., Li, X., Tu, Y., Yang, S., Van Horn, R.M., Ni, C., Pochan, D.J., Quirk, R.P., Wesdemiotis, C., Zhang, W.B. and Cheng, S.Z.D., J. Am. Chem. Soc., 2010, 132: 16741

    Article  CAS  Google Scholar 

  15. 15

    Zhang, W.B., Li, Y., Li, X., Dong, X., Yu, X., Wang, C.L., Wesdemiotis, C., Quirk, R.P. and Cheng, S.Z.D., Macromolecules, 2011: 2589

  16. 16

    He, J., Yue, K., Liu, Y., Yu, X., Ni, P., Cavicchi, K.A., Quirk, R.P., Chen, E.Q., Cheng, S.Z.D. and Zhang, W.B., Polym. Chem., 2012, 3: 2112

    Article  CAS  Google Scholar 

  17. 17

    Li, Y., Dong, X.H., Guo, K., Wang, Z., Chen, Z., Wesdemiotis, C., Quirk, R.P., Zhang, W.B. and Cheng, S.Z.D., ACS Macro. Lett., 2012, 1: 834

    Article  CAS  Google Scholar 

  18. 18

    Kolb, H.C., Finn, M.G. and Sharpless, K.B., Angew. Chem. Int. Ed., 2001, 40: 2004

    Article  CAS  Google Scholar 

  19. 19

    Iha, R.K., Wooley, K.L., Nystrom, A.M., Burke, D.J., Kade, M.J. and Hawker, C.J., Chem. Rev., 2009, 109: 5620

    Article  CAS  Google Scholar 

  20. 20

    Kempe, K., Krieg, A., Becer, C.R. and Schubert, U.S., Chem. Soc. Rev., 2012, 41: 176

    Article  CAS  Google Scholar 

  21. 21

    Meldal, M. and Tornøe, C.W., Chem. Rev., 2008, 108: 2952

    Article  CAS  Google Scholar 

  22. 22

    Hoyle, C.E. and Bowman, C.N., Angew. Chem. Int. Ed., 2010, 49: 1540

    Article  CAS  Google Scholar 

  23. 23

    Hoyle, C.E., Lowe, A.B. and Bowman, C.N., Chem. Soc. Rev., 2010, 39: 1355

    Article  CAS  Google Scholar 

  24. 24

    Lowe, A.B., Polym. Chem., 2010, 1: 17

    Article  CAS  Google Scholar 

  25. 25

    Gao, H. and Matyjaszewski, K., J. Am. Chem. Soc., 2007, 129: 6633

    Article  CAS  Google Scholar 

  26. 26

    Touris, A. and Hadjichristidis, N., Macromolecules, 2011, 44: 1969

    Article  CAS  Google Scholar 

  27. 27

    Sugai, N., Heguri, H., Ohta, K., Meng, Q.Y., Yamamoto, T. and Tezuka, Y., J. Am. Chem. Soc., 2010, 132: 14790

    Article  CAS  Google Scholar 

  28. 28

    Touris, A., Mays, J.W. and Hadjichristidis, N., Macromolecules, 2011, 44: 1886

    Article  CAS  Google Scholar 

  29. 29

    Wang, G.W., Hu, B., Fan, X.S., Zhang, Y.N. and Huang, J.L., J. Polym. Sci., Part A: Polym. Chem., 2012, 50: 2227

    Article  CAS  Google Scholar 

  30. 30

    Takano, A., Furutani, T. and Isono, Y., Macromolecules, 1994, 27: 7914

    Article  CAS  Google Scholar 

  31. 31

    Quirk, R.P., Wang, S.F., Foster, M.D., Wesdemiotis, C. and Yol, A.M., Macromolecules, 2011, 44: 7538

    Article  CAS  Google Scholar 

  32. 32

    Glotzer, S.C., Science, 2004, 306: 419

    Article  CAS  Google Scholar 

  33. 33

    Glotzer, S.C., Horsch, M.A., Iacovella, C.R., Zhang, Z., Chan, E.R. and Zhang, X., Curr. Opin. Colloid Interface Sci., 2005, 10: 287

    Article  CAS  Google Scholar 

  34. 34

    Yu, X., Zhang, W.B., Yue, K., Li, X., Liu, H., Xin, Y., Wang, C.L., Wesdemiotis, C. and Cheng, S.Z.D., J. Am. Chem. Soc., 2012, 134: 7780

    Article  CAS  Google Scholar 

  35. 35

    Dong, X.H., Zhang, W.B., Li, Y., Huang, M., Zhang, S., Quirk, R.P. and Cheng, S.Z.D., Polym. Chem., 2012, 3: 124

    Article  CAS  Google Scholar 

  36. 36

    Voronkov, M. and Lavrent’yev, V., Top. Curr. Chem., 1982, 102: 199

    Article  CAS  Google Scholar 

  37. 37

    Laine, R.M., J. Mater. Chem., 2005, 15: 3725

    Article  CAS  Google Scholar 

  38. 38

    Li, G., Wang, L., Ni, H. and Pittman, C.U., J. Inorg. Organomet. Polym., 2001, 11: 123

    Article  CAS  Google Scholar 

  39. 39

    Phillips, S.H., Haddad, T.S. and Tomczak, S.J., Curr. Opin. Solid State Mater. Sci., 2004, 8: 21

    Article  CAS  Google Scholar 

  40. 40

    Wu, J. and Mather, P.T., Polym. Rev., 2009, 49: 25

    Article  CAS  Google Scholar 

  41. 41

    Yue, K., Liu, C., Guo, K., Yu, X., Huang, M., Li, Y., Wesdemiotis, C., Cheng, S.Z.D. and Zhang, W.-B., Macromolecules, 2012, 45: 8126

    Article  CAS  Google Scholar 

  42. 42

    Yue, K., Liu, C., Guo, K., Wu, K., Dong, X.-H., Liu, H., Huang, M., Wesdemiotis, C., Cheng, S. Z. D. and Zhang, W.-B., Polym. Chem., 2012: DOI: 10.1039/C2PY20881D

  43. 43

    Gilman, H. and Cartledge, F.K., J. Organomet. Chem., 1964, 2: 447

    Article  CAS  Google Scholar 

  44. 44

    Hadjichristidis, N., Iatrou, H., Pispas, S. and Pitsikalis, M., J. Polym. Sci., Part A: Polym. Chem., 2000, 38: 3211

    Article  CAS  Google Scholar 

  45. 45

    Gunes, K., Isayev, A.I., Li, X.P. and Wesdemiotis, C., Polymer, 2010, 51: 1071

    Article  CAS  Google Scholar 

  46. 46

    Bellas, V. and Rehahn, M., Macromol. Chem. Phys., 2009, 210: 320

    Article  CAS  Google Scholar 

  47. 47

    Zhang, W.B., Tu, Y., Ranjan, R., van Horn, R.M., Leng, S., Wang, J., Polce, M.J., Wesdemiotis, C., Quirk, R.P., Newkome, G.R. and Cheng, S.Z.D., Macromolecules, 2008, 41: 515

    Article  CAS  Google Scholar 

  48. 48

    Li, Y., Hoskins, J.N., Sreerama, S.G. and Grayson, S.M., Macromolecules, 2010, 43: 6225

    Article  CAS  Google Scholar 

  49. 49

    Zhang, S., Li, A., Zou, J., Lin, L.Y. and Wooley, K.L., ACS Macro. Lett., 2012, 1: 328

    Article  CAS  Google Scholar 

  50. 50

    Zhang, Z.L., Horsch, M.A., Lamm, M.H. and Glotzer, S.C., Nano Lett., 2003, 3: 1341

    Article  CAS  Google Scholar 

  51. 51

    Horsch, M.A., Zhang, Z. and Glotzer, S.C., Phys. Rev. Lett., 2005, 95: 056105

    Article  Google Scholar 

  52. 52

    Iacovella, C.R., Horsch, M.A., Zhang, Z. and Glotzer, S.C., Langmuir, 2005, 21: 9488

    Article  CAS  Google Scholar 

  53. 53

    Glotzer, S.C. and Solomon, M.J., Nat. Mater., 2007, 6: 557

    Article  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Stephen Z. D. Cheng or Wen-Bin Zhang.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Yue, K., He, J., Liu, C. et al. Anionic synthesis of a “clickable” middle-chain azidefunctionalized polystyrene and its application in shape amphiphiles. Chin J Polym Sci 31, 71–82 (2013). https://doi.org/10.1007/s10118-013-1215-x

Download citation

Keywords

  • Living anionic polymerization
  • Polyhedral oligomeric silsesquioxane (POSS)
  • “Click” chemistry
  • General functionalization methodology (GFM)