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Synthesis and micellar behavior of poly(acrylic acid-b-styrene) block copolymers

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Abstract

Poly(acrylic acid-b-styrene) (PAA-b-PS) amphiphilic block copolymers were synthesized by consecutive telomerization of tert-butyl acrylate, atom transfer radical polymerization (ATRP) of styrene, and hydrolysis. The resulting block copolymers were characterized by 1H NMR and GPC. These amphiphilic block copolymeric micelles were prepared by dialysis against water. Transmission electron micrograph (TEM) and laser particle sizer measurements were used to determine the morphology and size of these micelles. The results showed that these amphiphilic block copolymers formed spherical micelles with average size of 140–190 nm. The critical micelle concentration (CMC) and the kinetic stability of these micelles were investigated by fluorescence technique, using pyrene as a fluorescence probe. The observed CMC value was in the range of 0.075–0.351 mg/L. Kinetic stability studies showed that the stability of micelles increased with the decrease of the pH value of the solution.

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References

  1. Alexandridis P, Lindman B (2000) Amphiphilic block copolymers―self-assembly and applications. Elsevier Science B.V, New York

    Google Scholar 

  2. Gast AP (1997) Polymeric micelles. Current Opinion in Colloid & Interface Science 2(3):258–263

    Article  CAS  Google Scholar 

  3. Kabanov AV, Chekhonin VP, Alakhov VY, Batrakova EV, Lebedev AS, Melik-Nubarov NS, Arzhakov SA, Levashov AV, Morozov GV, Severin ES, Kabanov VA (1989) The neuroleptic acitivity of haloperidol increases after its solubilization in surfactant micelles. Micelles as microcontainers for drug targeting. FEBS Lett 258:343–345

    Article  CAS  Google Scholar 

  4. Yokoyama M, Miyauchi M, Yamada N, Okano T, Sakurai Y, Kataoka K, Inoue S (1990) Polymer micelles as novel drug carrier: adriamycin-conjugated poly(ethylene glycol)-poly(aspartic acid) block copolymer. J Control Release 11(1–3):269–278

    CAS  Google Scholar 

  5. Hurter PN, Hatton TA (1992) Solubilization of polycyclic aromatic hydrocarbons by poly(ethylene oxide-propylene oxide) block copolymer micelles: effects of polymer structure. Langmuir 8(5):1291–1299

    Article  CAS  Google Scholar 

  6. Jones MC, Leroux JC (1999) Polymeric micelles―a new generation of colloidal drug carriers. Eur J Pharm Biopharm 48(2):101–111

    Article  CAS  Google Scholar 

  7. Mura JL, Riess G (1995) Polymeric surfactants in latex technology: polystyrene–poly(ethylene oxide) block copolymers as stabilizers in emulsion polymerization. Polymer for Adv Technol 6(7):497–508

    Article  CAS  Google Scholar 

  8. Rösler A, Vandermeulen GWM, Klok HA (2001) Advanced drug delivery devices via self-assembly of amphiphilic block copolymers. Advanced Drug Delivery Reviews 53(1):95–108

    Article  Google Scholar 

  9. Burguière C, Pascual S, Bui C, Vairon JP, Charleux B, Davis KA, Matyjaszewski K, Bétremieux I (2001) Block copolymers of polystyrene and poly(acrylic acid) of various molar masses, topologies, and compositions prepared via controlled/living radical polymerization. Application as stabilizers in emulsion polymerization. Macromolecules 34(13):4439–4450

    Article  Google Scholar 

  10. Nardin C, Widmer J, Winterhalter M, Meier W (2001) Amphiphilic block copolymer nanocontainers as bioreactors. Eur Phys J E 4(4):403–410

    Article  CAS  Google Scholar 

  11. Winnik FM, Regismond STA (1996) Fluorescence methods in the study of the interactions of surfactants with polymers. Colloids Surf, A Physicochem Eng Asp 118(1-2):1–39

    Article  CAS  Google Scholar 

  12. Hautekeer JP, Varshney SK, Fayt R, Jacobs C, Jérôme R, Teyssié P (1990) Anionic polymerization of acrylic monomers. 5. Synthesis, characterization, and modification of polystyrene-poly(tert-butyl acrylate) di- and triblock copolymers. Macromolecules 23(17):3893–3898

    Article  CAS  Google Scholar 

  13. Zhang LF, Eisenberg A (1996) Multiple morphologies and characteristics of “crew-cut” micelle-like aggregates of polystyrene-b-poly(acrylic acid) diblock copolymers in aqueous solutions. J Am Chem Soc 118:3168–3181

    Article  CAS  Google Scholar 

  14. Zhang LF, Eisenberg A (1996) Morphogenic effect of added ions on crew-cut aggregates of polystyrene- b-poly(acrylic acid) block copolymers in solutions. Macromolecules 19(27):8805–8815

    Article  Google Scholar 

  15. Burguière C, Chassenieux C, Charleux B (2003) Characterization of aqueous micellar solutions of amphiphilic block copolymers of poly(acrylic acid) and polystyrene prepared via ATRP. Toward the control of the number of particles in emulsion polymerization. Polymer 44(3):509–518

    Article  Google Scholar 

  16. Yue L, Zhang XB, Wu SK (2004) The synthesis of amphiphilic diblock copolymer PS-b-PAA and its morphology, nano-size aggregate formation in solutions. Acta Polymerica Sinica 2:236–239

    Google Scholar 

  17. Tang ZZ, Gao BJ, He SX (2005) Self-aggregation behavior of amphiphilic block copolymer PSt-b-PAA in toluene. Chemical Journal of Chinese Universities 26(12):2381–2385

    CAS  Google Scholar 

  18. Li GY, Shi LQ, Ye Q, Zhou WY, Tian JG (2006) Electric-field-assisted assembly and alignment of polystyrene-b-poly(acrylic acid) micelles. Colloid & Polym Sci 284:1179–1183

    Article  CAS  Google Scholar 

  19. Zhang WQ, Shi LQ, Miao ZJ, Wu K, An YL (2005) Core-shell-corona micellar complexes between poly(ethylene glycol)-block-poly(4-vinyl pyridine) and polystyrene-block-poly(acrylic acid). Macromol Chem Phys 206(23):2354–2361

    Article  CAS  Google Scholar 

  20. Guo FX, Jankova K, Schulte L, Vigild ME, Ndoni S (2008) One-step routes from di- and triblock copolymer precursors to hydrophilic nanoporous poly(acrylic acid)-b-polystyrene. Macromolecules 41(4):1486–1496

    Article  CAS  Google Scholar 

  21. Zhang Y, Xiao X, Zhou JJ, Wang L, Li ZB, Li L, Shi LQ, Chan CM (2009) Re-assembly behaviors of polystyrene-b-poly(acrylic acid) micelles. Polymer 50(25):6166–6171

    Article  CAS  Google Scholar 

  22. Xue YN, Huang ZZ, Zhang JT, Liu M, Zhang M, Huang SW, Zhuo RX (2009) Synthesis and self-assembly of amphiphilic poly(acrylic acid-b-DL-lactide) to form micelles for pH-responsive drug delivery. Polymer 50(15):3706–3713

    Article  CAS  Google Scholar 

  23. Li GH, Cho CG (2008) CMC and dynamic properties of poly(VA-b-St) copolymer micelles for drug delivery. Korean J Chem Eng 25(6):1444–1447

    Article  CAS  Google Scholar 

  24. Boutevin B (2000) From telomerization to living radical polymerization. J Polym Sci Part A: Polym Chem 38(18):3235–3243

    Article  CAS  Google Scholar 

  25. Destarac M, Pees B, Boutevin B (2000) Radical telomerization of vinyl acetate with chloroform. Application to the synthesis of poly(vinyl acetate)-block-polystyrene copolymers by consecutive telomerization and atom transfer radical polymerization. Macromol Chem Phys 201(11):1189–1199

    Article  CAS  Google Scholar 

  26. Li GH, Cho CG (2002) Synthesis and characterization of poly(vinyl alcohol-b-styrene) via atom transfer radical polymerization and saponification. Macromol Res 10(6):339–344

    Article  CAS  Google Scholar 

  27. Li GH, Yang PP, Zhao ZJ, Gao ZS, He LQ, Tong ZF (2011) Synthesis of poly(tert-butyl acrylate) telomer by free-radical telomerization. CIESC J 62(7):2061–2066

    CAS  Google Scholar 

  28. Destarac M, Bessiere JM, Boutevin B (1998) Atom transfer radical polymerization of styrene initiated by polychloroalkanes and CuCl/2,2′-bipyridine: a kinetic and mechanistic study. J Polym Sci: Polym Chem 36(16):2933–2947

    Article  CAS  Google Scholar 

  29. Paik HJ, Teodorescu M, Xia JH, Matyjaszewski K (1999) Block copolymerizations of vinyl acetate by combination of conventional and atom transfer radical polymerization. Macromolecules 32(21):7023–7031

    Article  CAS  Google Scholar 

  30. Kalyanasundaram K, Thomas JK (1977) Environmental effects on vibronic band intensities in pyrene monomer fluorescence and their application in studies of micellar systems. J Am Chem Soc 99(7):2039–2044

    Article  CAS  Google Scholar 

  31. Zhao CL, Winnik MA, Riess G, Croucher MD (1990) Fluorescence probe techniques used to study micelle formation in water-soluble block copolymers. Langmuir 6(2):514–516

    Article  CAS  Google Scholar 

  32. Cao T, Munk P, Ramireddy C, Tuzarlt Z, Webber SE (1991) Fluorescence studies of amphiphilic poly(methacrylic acid)-block-polystyrene-block-poly(methacrylic acid) micelles. Macromolecules 24(23):6300–6305

    Article  CAS  Google Scholar 

  33. Li GH, Cho CG (2005) Synthesis and micellar behavior of poly(vinyl alcohol-b-styrene) copolymers containing PVA blocks with different syndiotacticity. Colloid Polym Sci 283:946–953

    Article  CAS  Google Scholar 

  34. Sun XY, Zhou YF, Yan DY (2009) Drug release property of a pH-responsive double-hydrophilic hyperbranched graft copolymers. Sci China Ser B: Chem 52(10):1703–1710

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This research was supported by the National Nature Science Foundation of China (grant no. 21064001), and the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology.

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  1. Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, No. 100 Daxue East Road, Nanning, Guangxi, 530004, People’s Republic of China

    Guang Hua Li, Ping Ping Yang, Zhen Sheng Gao & Yuan Qin Zhu

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  1. Guang Hua Li
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  2. Ping Ping Yang
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Correspondence to Guang Hua Li.

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Li, G.H., Yang, P.P., Gao, Z.S. et al. Synthesis and micellar behavior of poly(acrylic acid-b-styrene) block copolymers. Colloid Polym Sci 290, 1825–1831 (2012). https://doi.org/10.1007/s00396-012-2799-3

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  • DOI: https://doi.org/10.1007/s00396-012-2799-3

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