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Synthesis of novel thermoresponsive micelles by graft copolymerization of N-isopropylacrylamide on poly(ε-caprolactone-co-α-bromo-ε-caprolactone) as macroinitiator via ATRP

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Abstract

α-Bromo-ε-caprolactone (α-BrCL) was synthesized from α-bromocyclohexanone by using 3-chloroperoxybenzoic acid. α-BrCL was then used as a comonomer in the ring-opening polymerization of ε-caprolactone (CL) initiated with aluminum isopropoxide to synthesize poly(CL-co-α-BrCL) copolymer. This copolymer was used as the macroinitiator in the atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAAm) for the synthesis of stimuli-responsive and biodegradable PCL-g-PNIPAAm copolymer. A core-shell type nano-structure was formed with a hydrophilic outer shell and a hydrophobic inner core from these copolymers, which exhibited a phase transition temperature around 31 °C. The copolymers were characterized by 1H-NMR and FT-IR spectroscopies. Number-average molecular weight of the poly(CL-co-α-BrCL) and PCL-g-PNIPAAm copolymers was calculated from corresponding 1H-NMR spectra to be 5770 and 6810 gmol−1, respectively. Thermal stability of the copolymer was investigated by thermogravimetric analysis (TGA) and crystallization behavior was studied by differential scanning calorimetry (DSC). Transmission electron microscopy (TEM) showed that the self-assemble micelle aggregates had well defined spherical shape. From the fluorescence spectra, fluorescence intensity of pyrene in the copolymer micelles increased and red-shifted as the copolymer concentration increases, indicating the formation of self-assemble polymeric micelles in water. The critical micelle concentration was found to be 3.2 × 10−3 mg/mL. TEM results showed that micelles have spherical shapes with a diameter of about 70 nm. The obtained micelles can be desirable for potential applications in biomedical fields, such as drug delivery systems.

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Authors and Affiliations

  1. Department of Chemistry, Payame Noor University, P.O. Box 19395-3697, Tehran, IR, Iran

    Bakhshali Massoumi & Samin Hamidi

  2. Polymer Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box: 14115-114, Tehran, IR, Iran

    Mahdi Abdollahi

  3. Laboratory of Polymer, Faculty of Chemistry, University of Tabriz, Tabriz, IR, Iran

    Marziyeh Fathi & Ali Akbar Entezami

Authors
  1. Bakhshali Massoumi
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  2. Mahdi Abdollahi
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  3. Marziyeh Fathi
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  4. Ali Akbar Entezami
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  5. Samin Hamidi
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Correspondence to Bakhshali Massoumi.

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Massoumi, B., Abdollahi, M., Fathi, M. et al. Synthesis of novel thermoresponsive micelles by graft copolymerization of N-isopropylacrylamide on poly(ε-caprolactone-co-α-bromo-ε-caprolactone) as macroinitiator via ATRP. J Polym Res 20, 47 (2013). https://doi.org/10.1007/s10965-012-0047-7

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  • DOI: https://doi.org/10.1007/s10965-012-0047-7

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