Citation: Xin-xin Li, Xiao Huo, Hui-jiao Han, Shao-liang Lin. Synthesis, Self-assembly and pH Sensitivity of a Novel Fluorinated Triphilic Block Copolymer[J]. Chinese Journal of Polymer Science, ;2017, 35(11): 1363-1372. doi: 10.1007/s10118-017-1963-0 shu

Synthesis, Self-assembly and pH Sensitivity of a Novel Fluorinated Triphilic Block Copolymer

a.
Key Laboratory of Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
b.
Key Laboratory of Advanced Polymeric Materials, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Xin-xin Li, xinxinli@ecust.edu.cn Shao-liang Lin, slin@ecust.edu.cn
Received Date: 12 March 2017
Revised Date: 7 April 2017
Accepted Date: 11 April 2017

Fund Project: Fundamental Research Funds for the Central Universities B14018Fundamental Research Funds for the Central Universities 222201717001Fundamental Research Funds for the Central Universities WD1616010the National Natural Science Foundation of China 51622301the National Natural Science Foundation of China 51573046

A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate (EHMA), tert-butyl methacrylate (tBMA) and 1H, 1H, 2H, 2H-perfluorodecyl acrylate (FA) (PEHMA-b-PtBMA-b-PFA) was first synthesized using three successive reversible addition fragmentation chain transfer (RAFT) polymerization and the subsequent hydrolyzing at acidic condition. The as-fabricated triblock copolymer exhibited an interesting morphology evolution from the multi-compartment rod-like structure to spherical structure along with the addition of a selective solution. At the same time, a visible phase separation domain could be seen in the core area due to the existence of fluorocarbon segments. Furthermore, the self-assembly behavior of the triphilic copolymer at different pH was also verified by transmission electron microscopy, as well as the dynamic light scattering. These stimuli-responsive multi-compartment nanostructures may have potential applications in drug delivery.
- Triphilic block copolymer,
- Self-assembly,
- pH sensitivity,
- Fluorinated copolymer,
- Multi-compartment structure
1. [1]
  Ulrich, K., Galvosas, P., Karger, J., Grinberg, F., Vernimmen, J., Meynen, V. and Cool, P., J. Phys. Chem. B, 2010, 114(12):4223 doi: 10.1021/jp907647n
2. [2]
  Wang, D.L., Tong, G.S., Dong, R.J., Zhou, Y.F., Shen, J. and Zhu, X.Y., Chem. Commun., 2014, 50(81):11994 doi: 10.1039/C4CC03155E
3. [3]
  Busseron, E., Ruff, Y., Moulin, E. and Giuseppone, N., Nanoscale, 2013, 5(16):7098 doi: 10.1039/c3nr02176a
4. [4]
  Wang, J.X., Zhang, Y.Z., Wang, S.T., Song, Y.L. and Jiang, L., Acc. Chem. Res., 2011, 44(6):405 doi: 10.1021/ar1001236
5. [5]
  Malhotra, S., Bauer, H., Tschiche, A., Staedtler, A.M., Mohr, A., Calderón, M., Parmar, V.S., Hoeke, L., Sharbati, S. and Einspanier, R., Biomacromolecules, 2012, 13(10):3087 doi: 10.1021/bm300892v
6. [6]
  Wang, Y. and Grayson, S.M., Adv. Drug Deliv. Rev., 2012, 64(9):852 doi: 10.1016/j.addr.2012.03.011
7. [7]
  Namazi, H. and Jafarirad, S., Int. J. Pharmaceut., 2011, 407(1-2):167 doi: 10.1016/j.ijpharm.2011.01.007
8. [8]
  Du, J.Z. and Armes, S.P., Langmuir, 2009, 25(16):9564 doi: 10.1021/la900834z
9. [9]
  He, J.L., Ni, P.H. and Liu, C.C., J. Polym. Sci., Part A:Polym. Chem., 2008, 46(9):3029 doi: 10.1002/(ISSN)1099-0518
10. [10]
  Marsat, J.N., Heydenreich, M., Kleinpeter, E., Berlepsch, H.V., Böttcher, C. and Laschewsky, A., Macromolecules, 2011, 44(7):2092 doi: 10.1021/ma200032j
11. [11]
  Skrabania, K., Berlepsch, H.V., Bottcher, C. and Laschewsky, A., Macromolecules, 2010, 43(1):271 doi: 10.1021/ma901913f
12. [12]
  Edmonds, W.F., Hillmyer, M.A. and Lodge, T.P., Macromolecules, 2007, 40(14):4917 doi: 10.1021/ma0704360
13. [13]
  Zhang, H., Ni, P.H., He, J.L. and Liu, C.C., Langmuir, 2008, 24(9):4647 doi: 10.1021/la704036a
14. [14]
  Berlepsch, H.V., Bottcher, C., Skrabania, K. and Laschewsky, A., Chem. Commun., 2009, 17(17):2290
15. [15]
  Wu, Y.C., Bastakoti, B.P., Pramanik, M., Yamauchi, Y. and Kuo, S.W., Polym. Chem., 2015, 6(28):5110 doi: 10.1039/C5PY00663E
16. [16]
  Saito, N., Liu, C., Lodge, T.P. and Hillmyer, M.A., ACS Nano, 2010, 4(4):1907 doi: 10.1021/nn9016873
17. [17]
  Skrabania, K., Laschewsky, A., Berlepsch, H.V. and Bottcher, C., Langmuir, 2009, 25(13):7594 doi: 10.1021/la900253j
18. [18]
  Li, S., He, J.L., Zhang, M.Z., Wang, H.R. and Ni, P.H., Polym. Chem., 2016, 7(9):1773 doi: 10.1039/C5PY02017D
19. [19]
  Chen, J., Li, J.J. and Luo, Z.H., Polym. Chem., 2013, 51(5):1107 doi: 10.1002/pola.26473
20. [20]
  Li, X.X., Yang, Y.H., Li, G.J. and Lin, S.L., Polym. Chem., 2014, 5(15):4553 doi: 10.1039/C4PY00308J
21. [21]
  Price, E.W., Guo, Y.Y., Wang, C.W. and Moffitt, M.G., Langmuir, 2009, 25(11):6398 doi: 10.1021/la804317s
22. [22]
  Fang, B., Walther, A., Wolf, A., Xu, Y.Y., Yuan, J.Y. and Muller, A.H.E., Angew. Chem. Int. Ed., 2009, 48(16):2877 doi: 10.1002/anie.200806051
23. [23]
  Laschewsky, A., Curr. Opin. Colloid Interface Sci., 2003, 8(3):274 doi: 10.1016/S1359-0294(03)00049-9
24. [24]
  Jiang, Y.J., Li, L., Liu, J.P., Wang, R., Wang, H.S., Tian, Q. and Li, X.Y., J. Flu. Chem., 2016, 183:82 doi: 10.1016/j.jfluchem.2016.01.010
25. [25]
  Gao, Y., Li, X.Y., Hong, L.Z. and Liu, G.J., Macromolecules, 2012, 45(3):1321 doi: 10.1021/ma202084m
26. [26]
  Kyeremateng, S.O., Busse, K., Kohlbrecher, J. and Kressler, J., Macromolecules, 2011, 44(3):583 doi: 10.1021/ma102232z
27. [27]
  Rinkenauer, A.C., Schallon, A., Gunther, U., Wagner, M., Betthausen, E., Schubert, U.S. and Schacher, F.H., ACS Nano, 2013, 7(11):9621 doi: 10.1021/nn402072d
28. [28]
  Synatschke, C.V., Nomoto, T., Cabral, H., Fortsch, M., Toh, K., Matsumoto, Y., Miyazaki, K., Hanisch, A., Schacher, F.H., Kishimura, A., Nishiyama, N., Muller, A.H.E. and Kataoka, K., ACS Nano, 2014, 8(2):1161 doi: 10.1021/nn4028294
29. [29]
  Nystrom, A.M., Bartels, J.W., Du, W. and Wooley, K.L., J. Polym. Sci., Part A:Polym. Chem., 2009, 47(4):1023 doi: 10.1002/pola.v47:4
30. [30]
  Muraro, P.I.R., Freitas, A.G.O., Trindade, S.G., Giacomelli, F.C., Bonvent, J.J., Schmidt, V.C. and Giacomelli, F.P., J. Flu. Chem., 2014, 168:251 doi: 10.1016/j.jfluchem.2014.10.017
31. [31]
  Semsarilar, M., Ladmiral, V., Blanazs, A. and Armes, S.P., Polym. Chem., 2014, 5(10):3466 doi: 10.1039/C4PY00201F
32. [32]
  Wang, T., Kuang, M.X., Jin, F., Cai, J.H., Shi, L., Zheng, Y.M., Wang, J.X. and Jiang, L., Chem. Commun., 2016, 52(18):3619 doi: 10.1039/C5CC10233B
33. [33]
  Lai, J.T., Filla, D. and Shea, R., Macromolecules, 2002, 35(18):6754 doi: 10.1021/ma020362m
34. [34]
  Li, X.X., Fang, B., Lin, S., Wu, P.P. and Han, Z.W., Acta Polymerica Sinica (in Chinese), 2003, (6):910
35. [35]
  Wang, Y.Y., Lin, S.L., Zhang, M.H., Xing, Y.H., He, X.H., Lin, J.P. and Chen, T., Soft Matter, 2012, 8(11):3131 doi: 10.1039/c2sm07100b
36. [36]
  Crisci, A., Hay, D.N.T., Sonke, S. and Firestone, M.A., Macromol. Symp., 2009, 281(1):126 doi: 10.1002/masy.v281:1
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1.
沈阳化工大学材料科学与工程学院沈阳 110142