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Preparation and characterization of thermoresponsive hyperbranched polyethylenimine with plenty of reactive primary amine groups

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Abstract

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 HPEIIBAm0.80 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 (T cp) 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 T cp was around 8.5. Moreover, HPEI-IBAm0.8-NH2 showed higher T cp 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.

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Authors and Affiliations

  1. Department of Chemistry, School of Sciences, Tianjin University; Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, China

    Hua-ji Liu, Run-hua Dong & Yu Chen  (陈宇)

Authors
  1. Hua-ji Liu
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  2. Run-hua Dong
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  3. Yu Chen  (陈宇)
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Corresponding author

Correspondence to Yu Chen  (陈宇).

Additional information

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).

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Liu, Hj., Dong, Rh. & Chen, Y. Preparation and characterization of thermoresponsive hyperbranched polyethylenimine with plenty of reactive primary amine groups. Chin J Polym Sci 32, 961–968 (2014). https://doi.org/10.1007/s10118-014-1471-4

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  • DOI: https://doi.org/10.1007/s10118-014-1471-4

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