Advertisement

Polymer Bulletin

, Volume 70, Issue 11, pp 3201–3220 | Cite as

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

  • Avnish Kumar Mishra
  • K. Ramesh
  • Tapas Kumar Paira
  • Divesh N. Srivastava
  • Tarun Kumar Mandal
  • Nira Misra
  • Biswajit RayEmail author
Original Paper

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.

Keywords

Silver Nanoparticles Block Copolymer Xanthate Amphiphilic Block Copolymer Star Block Copolymer 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

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.

Supplementary material

289_2013_1017_MOESM1_ESM.doc (56 kb)
Supplementary material 1 (DOC 56 kb)

References

  1. 1.
    Ouchi M, Terashima T, Sawamoto M (2009) Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis. Chem Rev 109:4963–5050CrossRefGoogle Scholar
  2. 2.
    Yamago S (2009) Precision polymer synthesis by degenerative transfer controlled/living radical polymerization using organotellurium, organostibine, and organobismuthine chain transfer agents. Chem Rev 109:5051–5068CrossRefGoogle Scholar
  3. 3.
    Chiefari J, Mayadunne RTA, Moad G, Rizzardo E, Thang SH (1999) Polymerization process with living characteristics and polymers made therefrom. PCT Int Appl W099/31144Google Scholar
  4. 4.
    Coessens V, Pintave T, Matyzaszewski K (2001) Functional polymers by atom transfer radical polymerization. Prog Polym Sci 26:337–377CrossRefGoogle Scholar
  5. 5.
    Wan D, Satoh K, Kamigaito M, Okamoto Y (2005) Xanthate-mediated radical polymerization of N-vinylpyrrolidone in fluoroalcohols for simultaneous control of molecular weight and tacticity. Macromolecules 38:10397–10405CrossRefGoogle Scholar
  6. 6.
    Devasia R, Bindu RL, Mougia N, Gnanou Y (2005) Controlled radical polymerization of N-vinylpyrrolidone by reversible addition-fragmentation. Macromol Sympo 229:8–17CrossRefGoogle Scholar
  7. 7.
    Bilalis P, Pitsikalis M, Hadjichristidis N (2006) Controlled nitroxide-mediated and reversible addition-fragmentation chain transfer polymerization of N-vinylpyrrolidone: synthesis of block copolymers with styrene and 2-vinylpyridine. J Polym Sci Part A Polym Chem 44:659–665CrossRefGoogle Scholar
  8. 8.
    Yamago S, Ray B, Iida K, Yoshida JI, Tada T, Yoshizawa K, Kwak Y, Goto A, Fukuda T (2004) Highly versatile organostibine mediators for living radical polymerization. J Am Chem Soc 126:13908–13909CrossRefGoogle Scholar
  9. 9.
    Ray B, Kotani M, Yamago S (2006) Highly controlled synthesis of poly(N-vinylpyrrolidone) and its block copolymers by organostibine-mediated living radical polymerization. Macromolecules 39:5259–5265CrossRefGoogle Scholar
  10. 10.
    Yusa SI, Yamago S, Sugahara M, Morikawa S, Yamamoto T, Morishima Y (2007) Thermoresponsive diblock copolymers of poly(N-isopropylacrylamide) and poly(N-vinyl-2-pyrroridone) synthesized via organotellurium-mediated controlled radical polymerization (TERP). Macromolecules 40:5907–5915CrossRefGoogle Scholar
  11. 11.
    Yamago S, Kayahara E, Kotani M, Ray B, Kwak Y, Goto A, Fukuda T (2007) Highly controlled living radical polymerization through dual activation of organobismuthines. Angew Chem Intl Ed 46:1304–1306CrossRefGoogle Scholar
  12. 12.
    Lu X, Gong S, Meng L, Li C, Yang S, Zhang L (2007) Controllable synthesis of poly(N-vinylpyrrolidone) and its block copolymers by atom transfer radical polymerization. Polymer 48:2835–2842CrossRefGoogle Scholar
  13. 13.
    Pound G, Eksteen Z, Pfukwa R, McKenzie JM, Lange RFM, Klumperman B (2008) Unexpected reactions associated with the xanthate-mediated polymerization of N-vinylpyrrolidone. J Polym Sci Part A Polym Chem 46:6575–6593CrossRefGoogle Scholar
  14. 14.
    Pound G, Aguesse F, McLeary JB, Lange RFM, Klumperman B (2007) Xanthate-mediated copolymerization of vinyl monomers for amphiphilic and double-hydrophilic block copolymers with poly(ethylene glycol). Macromolecules 40:8861–8871CrossRefGoogle Scholar
  15. 15.
    Patel VK, Mishra AK, Viswakarma NK, Biswas CS, Ray B (2010) (S)-2-(Ethyl propionate)-(O-ethyl xanthate) and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of N-vinylpyrrolidone. Polym Bull 65:97–110CrossRefGoogle Scholar
  16. 16.
    Lele BS, Leroux JC (2002) Synthesis and micellar characterization of novel amphiphilic A-B-A triblock copolymers of N-(2-hydroxypropyl)methacrylamide or N-vinyl-2-pyrrolidone with poly(ε-caprolactone). Macromolecules 35:6714–6723CrossRefGoogle Scholar
  17. 17.
    Chung TW, Cho KY, Lee H-C, Nah JW, Yeo JH, Akaike T, Cho CS (2004) Novel micelle-forming block copolymer composed of poly (ε-caprolactone) and poly(vinyl pyrrolidone). Polymer 45:1591–1597CrossRefGoogle Scholar
  18. 18.
    Bartolozzi I, Solaro R, Schacht E, Chiellini E (2007) Hydroxyl end-capped macromers of N-vinyl-2-pyrrolidinone as precursors of amphiphilic block copolymers. Eur Polym J 43:4628–4638CrossRefGoogle Scholar
  19. 19.
    Levia A, Quina FH, Araneda E, Gargallo L, Radić D (2007) New three-arm amphiphilic and biodegradable block copolymers composed of poly(ε-caprolactone) and poly(N-vinyl-2-pyrrolidone). Synthesis, characterization and self-assembly in aqueous solution. J Coll Interf Sci 310:136–143CrossRefGoogle Scholar
  20. 20.
    Jeon HJ, You YC, Youk JH (2009) Synthesis and characterization of amphiphilic poly(N-vinylpyrrolidone)-b-poly(ε-caprolactone) copolymers by a combination of cobalt-mediated radical polymerization and ring-opening polymerization. J Polym Sci Part A Polym Chem 47:3078–3085CrossRefGoogle Scholar
  21. 21.
    Mishra AK, Patel VK, Viswakarma NK, Biswas CS, Raula M, Misra A, Mandal TK, Ray B (2011) Synthesis of well-defined amphiphilic poly(ε-caprolactone)-b-poly(N-vinylpyrrolidone) block copolymers via the combination of ROP and xanthate-mediated RAFT polymerization. Macromolecules 44:2465–2473CrossRefGoogle Scholar
  22. 22.
    Zhai C, Liu X, Yuan J, Gao Q (2013) Synthesis, characterization, and drug delivery research of an amphiphilic biodegradable star-shaped block copolymer. Polym Bull 70:419–429CrossRefGoogle Scholar
  23. 23.
    Paira TK, Banerjee S, Raula M, Kotal A, Si S, Mandal TK (2010) Peptide–polymer bioconjugates via atom transfer radical polymerization and their solution aggregation into hybrid micro/nanospheres for dye uptake. Macromolecules 43:4050–4061CrossRefGoogle Scholar
  24. 24.
    Štěpánek P (1993) In: Brown W (ed) Dynamic light scattering—the method and some applications. Clarendon, Boston, pp 177–241Google Scholar
  25. 25.
    Chu B (1991) Laser light scattering: basic principles and practices, 2nd edn. Academic Press, New York, pp 13–61Google Scholar
  26. 26.
    Cheng J, Ding J-X, Wang Y-C, Wang J (2008) Synthesis and characterization of star-shaped block copolymer of poly-(ε-caprolactone) and poly(ethyl ethylene phosphate) as drug carrier. Polymer 49:4784–4790CrossRefGoogle Scholar
  27. 27.
    Ramesh K, Mishra AK, Patel VK, Viswakarma NK, Biswas CS, Paira TK, Mandal TK, Maiti P, Misra N, Ray B (2012) Synthesis of well-defined amphiphilic poly(d, l-lactide)-b-poly(N-vinylpyrrolidone) block copolymers using ROP and xanthate-mediated RAFT polymerization. Polymer 53:5743–5753CrossRefGoogle Scholar
  28. 28.
    Chung TW, Cho KY, Lee HC, Nah JW, Yeo JH, Akaike T, Cho CS (2004) Novel micelle-forming block copolymer composed of poly (ε-caprolactone) and poly(vinyl pyrrolidone). Polymer 45:1591–1597CrossRefGoogle Scholar
  29. 29.
    Sheng YJ, Wang TY, Chen WM, Tsao HK (2007) A–B diblock copolymer micelles: effects of soluble-block length and component compatibility. J Phys Chem B 111:10938–10945CrossRefGoogle Scholar
  30. 30.
    Chatterjee U, Jewrajka SK, Guha S (2009) Dispersion of functionalized silver nanoparticles in polymer matrices: stability, characterization, and physical properties. Poly Compos 30:827–834CrossRefGoogle Scholar
  31. 31.
    Sakai T, Alexandridis P (2005) Mechanism of gold metal ion reduction, nanoparticle growth and size control in aqueous amphiphilic block copolymer solutions at ambient conditions. J Phys Chem B 109:7766–7777CrossRefGoogle Scholar
  32. 32.
    Vishwakarma NK, Mishra AK, Mishra A, Paira T, Patel VK, Biswas CS, Mandal TK, Maiti P, Ray B (2013) Synthesis, characterization, and application of novel amphiphilic poly(d-gluconamidoethyl methacrylate)-b-polyurethane-b-poly(d-gluconamidoethyl methacrylate) triblock copolymers. J Appl Polym Sci 128:1369–1380Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Avnish Kumar Mishra
    • 1
  • K. Ramesh
    • 1
    • 2
  • Tapas Kumar Paira
    • 3
  • Divesh N. Srivastava
    • 4
  • Tarun Kumar Mandal
    • 3
  • Nira Misra
    • 2
  • Biswajit Ray
    • 1
    Email author
  1. 1.Department of Chemistry, Faculty of ScienceBanaras Hindu UniversityVaranasiIndia
  2. 2.School of Biomedical EngineeringIndian Institute of Technology, Banaras Hindu UniversityVaranasiIndia
  3. 3.Polymer Science UnitIndian Association for the Cultivation of ScienceKolkataIndia
  4. 4.Central Salt and Marine Chemicals Research Institute (CSIR)BhavnagarIndia

Personalised recommendations