Preparation and Characterization of Thermoresponsive Hyperbranched Polyethylenimine with Plenty of Reactive Primary Amine Groups

Hua-ji Liu Run-hua Dong Yu Chen

Citation:  Hua-ji Liu, Run-hua Dong, Yu Chen. Preparation and Characterization of Thermoresponsive Hyperbranched Polyethylenimine with Plenty of Reactive Primary Amine Groups[J]. Chinese Journal of Polymer Science, 2014, 32(7): 961-968. doi: 10.1007/s10118-014-1471-4 shu

Preparation and Characterization of Thermoresponsive Hyperbranched Polyethylenimine with Plenty of Reactive Primary Amine Groups

    通讯作者: Yu Chen, chentangyu@yahoo.com
  • 基金项目:

    This work was financially supported by the financial support from the Program for New Century Excellent Talents in Universities, and the National Natural Science Foundation of China (Nos. 20804027 and 21274106).

摘要: Certain amount of primary amine (NH2) groups of hyperbranched polyethylenimine (HPEI) was first protected by Boc groups. Subsequently, the residual reactive amine groups were reacted with isobutyric anhydride to introduce isobutyramide (IBAm) groups to HPEI. Finally, Boc groups were deprotected to result in HPEI-IBAm-NH2 with 18% of primary amine terminals on the periphery and 80% of IBAm terminal groups (abbreviated as HPEI-IBAm0.80-NH2). 1H-NMR characterization proved the successful preparation of the product in each step. Compared with its spatial isomer HPEI-IBAm0.80 without primary amine groups, 1H-NMR spectra verified that more IBAm groups were located in the interior of HPEI-IBAm0.80-NH2. The further modification of HPEI-IBAm0.80-NH2 and HPEI-IBAm0.80 with p-nitrobenzaldehyde demonstrated that HPEI-IBAm0.80-NH2 was more reactive than HPEI-IBAm0.80 due to its possession of primary amines. Turbidimetry measurements showed that HPEI-IBAm0.80-NH2 was thermoresponsive in water. In the pH range of 9.5-10 its cloud point temperature (Tcp) was constant, and it increased obviously upon decreasing the pH below 9.5. The thermoresponsive HPEI-IBAm0.8 exhibited the similar trend, but the pH threshold to achieve the constant Tcp was around 8.5. Moreover, HPEI-IBAm0.8-NH2 showed higher Tcp and broader phase transition than HPEI-IBAm0.8. The mechanism leading to the different thermoresponsive properties between HPEI-IBAm0.8-NH2 and its spatial isomer HPEI-IBAm0.8 was discussed.

English


    1. [1]

      Galaev, I.Y. and Mattiasson, B., Trends Biotechnol., 1999, 17: 335

    2. [2]

      Weber, C., Hoogenboom, R. and Schubert, U.S., Prog. Polym. Sci., 2012, 37: 686

    3. [3]

      Hu, H.Y., Du, J., Meng, Q.B., Li, Z.Y. and Zhu, X.X., Chinese J. Polym. Sci., 2008, 26(2): 187

    4. [4]

      Yue, G.L., Cui, Q.L., Zhang, Y.X., Wang, E.J. and Wu, F.P., Chinese J. Polym. Sci., 2012, 30(5): 770

    5. [5]

      Haba, Y., Harada, A., Takagishi, T. and Kono, K., J. Am. Chem. Soc., 2004, 126: 12760

    6. [6]

      Tono, Y., Kojima, C., Haba, Y., Takahashi, T., Harada, A., Yagi, S. and Kono, K., Langmuir, 2006, 22: 4920

    7. [7]

      Haba, Y., Kojima, C., Harada, A. and Kono, K., Macromolecules, 2006, 39: 7451

    8. [8]

      Aathimanikandan, S.V., Savariar, E.N. and Thayumanavan, S., J. Am. Chem. Soc., 2005, 127: 14922

    9. [9]

      Jia, Z., Chen, H., Zhu, X. and Yan, D., J. Am. Chem. Soc., 2006, 128: 8144

    10. [10]

      Shen, Y., Kuang, M., Shen, Z., Nieberle, J., Duan, H. and Frey, H., Angew. Chem. Int. Ed., 2008, 47: 2227

    11. [11]

      Yang, J., Hu, D.D. and Zhang, H., React. Funct. Polym., 2012, 72: 438

    12. [12]

      Hassan, C.M. and Peppas, N.A., Adv. Polym. Sci., 2000, 153: 37

    13. [13]

      Schmer, M., Seiwert, J. and Frey, H., ACS Macro Lett., 2012, 1: 888

    14. [14]

      Liu, Y., Liu, X.Y., Liu, H.J., Cheng, F. and Chen, Y., Macromol. Res., 2012, 20: 578

    15. [15]

      Liu, H., Chen, Y. and Shen, Z., J. Polym. Sci. Part A: Polym. Chem., 2007, 45: 1177

    16. [16]

      Qin, H.W., Liu, H.J. and Chen, Y., Chinese J. Polym. Sci., DOI: 10.1007/s10118-014-1475-0

    17. [17]

      Wang, R.C., Fu, X.B., Liu, X., Liu, H.J., Chen, Y. and Cui, J., RSC Adv., 2013, 3: 17016

    18. [18]

      Liu, X., Cheng, F., Liu, H. and Chen, Y., Soft Matter, 2008, 4: 1991

    19. [19]

      Liu, X.Y., Mu, X.R., Liu, Y., Liu, H.J., Chen, Y., Cheng, F. and Jiang, S.C., Langmuir, 2012, 28: 4867

    20. [20]

      Mu, X.R., Tong, J.G., Liu, Y., Liu, X.Y., Liu, H.J. and Chen, Y., Polymer, 2013, 54: 2341

    21. [21]

      Boussif, O., Lezoualch, F., Zanta, M. A., Mergny, M. D., Scherman, D., Demeneix, B. and Behr, J.P., Proc. Natl. Acad. Sci., 1995, 92: 7297

    22. [22]

      Godbey, W.T., Wu, K.K. and Mikos, A.G., Proc. Natl. Acad. Sci., 1999, 96: 5177

    23. [23]

      Godbey, W.T., Barry, M.A., Saggau, P., Wu, K.K. and Mikos, A.G., J. Biomed. Mater. Res., 2000, 51: 321

    24. [24]

      Liu, X.Y., Cheng, F., Liu, Y., Liu, H.J. and Chen, Y., J. Mater. Chem., 2010, 20: 360

    25. [25]

      Liu, X.Y., Cheng, F., Liu, Y., Li, W.G., Chen, Y., Pan, H. and Liu, H.J., J. Mater. Chem., 2010, 20: 278

    26. [26]

      Zhang, J., Liu, H.J., Yuan, Y., Jiang, S., Yao, Y. and Chen, Y., ACS Macro Lett., 2013, 2: 67

    27. [27]

      Yin, J.Y., Liu, H.J., Jiang, S., Chen, Y. and Yao, Y., ACS Macro Lett., 2013, 2: 1033

    28. [28]

      Liu, H., Shen, Z., Stiriba, S.E., Chen, Y., Zhang, W. and Wei, L., J. Polym. Sci. Part A: Polym. Chem., 2006, 44: 4165

    29. [29]

      Jiang, S., Yao, Y., Chen, Q. and Chen, Y., Macromolecules, 2013, 46: 9688

    30. [30]

      Bloksma, M.M., Bakker, D.J., Weber, C., Hoogenboom, R. and Schubert, U.S., Macromol. Rapid Commun., 2010, 31: 724

    31. [31]

      Borkovec, M. and Koper, G.J.M., Macromolecules, 1997, 30: 2151

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  • 发布日期:  2014-07-05
  • 收稿日期:  2014-03-13
  • 修回日期:  2014-04-14
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