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Synthesis and self-assembly properties of well-defined four-arm star poly(ε-caprolactone)-b-poly(N-vinylpyrrolidone) amphiphilic block copolymers

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Abstract

Well-defined amphiphilic four-arm star diblock copolymers of poly(ε-caprolactone) (PCL) and poly(N-vinylpyrrolidone) (PNVP) have successfully been synthesized by combining the ring-opening polymerization (ROP) of ε-caprolactone (CL) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of N-vinylpyrrolidone (NVP). The resulting block copolymer shows the formation of spherical micelles in water as revealed by transmission electron microscopy (TEM) and supported by light-scattering study. The critical micellar concentration (cmc) value of the micelle increases with the increase in the PNVP block length. Hydrodynamic diameter distribution of the micelles decreases with the increase in the PNVP block length. The effective hydrodynamic ratio (R h) remains almost constant over the angles of scattering measurements above the corresponding cmc value. The usefulness of the synthesized star amphiphilic block copolymers was checked by the successful synthesis of silver nanoparticles.

Graphical abstract

Well-defined four-arm star poly(ε-caprolactone)-b-poly(N-vinylpyrrolidone) amphiphilic block copolymers are prepared by the combination of ring opening polymerization and xanthate-mediated reversible addition-fragmentation chain transfer polymerization and their self-assembly properties are studied using 1H NMR, fluorescence spectroscopy, dynamic light scattering, and TEM.

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Acknowledgments

The authors gratefully acknowledge the financial support from the Department of Science and Technology, Government of India, through grant no. SR/S1/PC-25/2006. V.K.P., N.K.V., and A.K.M., acknowledge CSIR, Government of India for research fellowships.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, 221005, India

    Avnish Kumar Mishra, K. Ramesh & Biswajit Ray

  2. School of Biomedical Engineering, Indian Institute of Technology, Banaras Hindu University, Varanasi, 221005, India

    K. Ramesh & Nira Misra

  3. Polymer Science Unit, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700 032, India

    Tapas Kumar Paira & Tarun Kumar Mandal

  4. Central Salt and Marine Chemicals Research Institute (CSIR), G. B. Marg, Bhavnagar, Gujarat, 364021, India

    Divesh N. Srivastava

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  1. Avnish Kumar Mishra
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  2. K. Ramesh
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  3. Tapas Kumar Paira
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  4. Divesh N. Srivastava
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  5. Tarun Kumar Mandal
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  6. Nira Misra
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  7. Biswajit Ray
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Correspondence to Biswajit Ray.

Electronic supplementary material

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Supporting Information. Synthesis of four-arm star S-(PCL21-b-PNVP28)4, S-(PCL21-b-PNVP37)4, and S-(PCL21-b-PNVP46)4 block copolymers, light-scattering and fluorescence spectroscopy data of polymers

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Mishra, A.K., Ramesh, K., Paira, T.K. et al. Synthesis and self-assembly properties of well-defined four-arm star poly(ε-caprolactone)-b-poly(N-vinylpyrrolidone) amphiphilic block copolymers. Polym. Bull. 70, 3201–3220 (2013). https://doi.org/10.1007/s00289-013-1017-x

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