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Formation of mesoglobules in aqueous media from thermo-sensitive poly(ethoxytriethyleneglycol acrylate)

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Abstract

A series of six poly(ethoxytriethyleneglycol acrylate) (PETEGA) homopolymers were synthesized by atom transfer radical polymerization, reversible addition-fragmentation transfer polymerization, and anionic polymerization in order to cover a molecular weight range from 7,000 to 40,000 Da. The polymers exhibited a lower critical solution temperature (LCST) behavior in water, which was observed by the occurrence of a cloud point (CP) at around 35 °C. The transmittance of visible light versus temperature dependence overlapped during the cooling and the heating cycles, showing almost a complete lack of hysteresis. Moreover, instead of the occurrence of an uncontrolled macroscopic phase separation, stable colloidal aggregates (mesoglobules) of narrow distribution in particle size were formed in water at temperatures above the LCST of PETEGA at 1 g L−1 solutions. The dimensions of the mesoglobules ranged from 91 to 235 nm, and particle size was not influenced by the molecular weight of PETEGA. Temperature changes caused considerable variations of the mesoglobules dimensions, which were smaller at higher temperatures. The addition of an anionic surfactant simultaneously increased the CP values by 4–6 °C and lowered the dimensions of the mesoglobules.

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References

  1. Aseyev V, Tenhu H, Winnik FM (2006) Temperature dependence of the colloidal stability of neutral amphiphilic polymers in water. Adv Polym Sci 196:1–61

    Article  CAS  Google Scholar 

  2. Aseyev V, Hietala S, Laukkanen A, Nuopponen M, Confortini O, Du Prez FE, Tenhu H (2005) Mesoglobules of thermoresponsive polymers in dilute aqueous solutions above the LCST. Polymer 46:7118–7131

    Article  CAS  Google Scholar 

  3. Trzebicka B, Weda P, Utrata-Wesolek A, Dworak A, Tsvetanov CB (2010) Mesoglobules of random copolyethers as templates for nanoparticles. J Polym Sci A 48:4074–4083

    Article  CAS  Google Scholar 

  4. Holmberg K, Jönsson B, Kronberg B, Lindman B (2003) In: Surfactants and polymers in aqueous solution, 2nd ed. Wiley, Chichester

  5. Weda P, Trzebicka B, Dworak A, Tsvetanov CB (2008) Thermosensitive nanospheres of low-density core—an approach to hollow nanoparticles. Polymer 49:1467–1474

    Article  CAS  Google Scholar 

  6. Dimitrov P, Toncheva N, Weda P, Rangelov S, Trzebicka B, Dworak A, Tsvetanov CB (2009) Nano-templates from thermoresponsive poly(ethoxytriethyleneglycol acrylate) for polymeric nano-capsules. Macromol Symp 278:89–95

    Article  CAS  Google Scholar 

  7. Kurosawa M, Yokoyama M, Okano T (2000) Gene expression control by temperature with thermo-responsive polymeric gene carriers. J Control Release 69:127–137

    Article  Google Scholar 

  8. Yokoyama M, Kurosawa M, Okano T (2001) Influential factors on temperature-controlled gene expression using thermoresponsive polymeric gene carriers. J Artif Organs 4:138–145

    Article  CAS  Google Scholar 

  9. Jiang X, Lavender CA, Woodcock JW, Zhao B (2008) Multiple micellization and dissociation transitions of thermo- and light-sensitive poly(ethylene oxide)-b-poly(ethoxytri(ethylene glycol) acrylate-co-o-nitrobenzyl acrylate) in water. Macromolecules 41:2632–2643

    Article  CAS  Google Scholar 

  10. Bouhadir G, Legrand N, Quiclet-Sire B, Zard SZ (1999) A new practical synthesis of tertiary S-alkyl dithiocarbonates and related derivatives. Tetrahedron Lett 40:277–280

    Article  CAS  Google Scholar 

  11. Antoun S, Teyssié P, Jérôme R (1997) Lithium diisopropylamide as initiator for the anionic polymerization of methacrylates. Macromolecules 30:1556–1561

    Article  CAS  Google Scholar 

  12. Antoun S, Teyssié P, Jérôme R (1997) Anionic polymerization of methacrylate monomers initiated by lithium dialkylamides. J Polym Sci A 1997(35):3637–3644

    Article  Google Scholar 

  13. Provencher SW (1979) Inverse problems in polymer characterization: direct analysis of polydispersity with photon correlation spectroscopy. Macromol Chem 180:201–209

    Article  CAS  Google Scholar 

  14. Afroze F, Nies E, Berghmans H (2000) Phase transitions in the system poly(N-isopropylacrylamide)/water and swelling behavior of the corresponding networks. J Mol Struct 554(1):55–68

    Article  CAS  Google Scholar 

  15. Lutz J-F, Akdemir O, Hoth A (2006) Point by point comparison of two thermosensitive polymers exhibiting a similar LCST: Is the age of poly(NIPAM) over? J Am Chem Soc 128:13046–13047

    Article  CAS  Google Scholar 

  16. Lutz J-F, Hoth A (2006) Preparation of ideal PEG analogues with a tunable thermosensitivity by controlled radical copolymerization of 2-(2-methoxyethoxy)ethyl methacrylate and oligo(ethylene glycol) methacrylate. Macromolecules 39:893–896

    Article  CAS  Google Scholar 

  17. Dong H, Matyjaszewski K (2010) Thermally responsive P(M(EO)2MA-co-OEOMA) copolymers via AGET ATRP in miniemulsion. Macromolecules 43:4623–4628

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Financial support by the National Science Fund of Bulgaria under grant DO 02-247/2008 is acknowledged. B.R., B.T., and A.D. gratefully acknowledge the financial support from the Ministry of Science and Higher Education of Poland, Grant NN 209 144136. The study benefited from the bilateral cooperation between the Polish and Bulgarian groups.

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Authors and Affiliations

  1. Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev 103-A, 1113, Sofia, Bulgaria

    Natalia Toncheva-Moncheva, Philip Dimitrov, Christo B. Tsvetanov & Stanislav Rangelov

  2. Centre of Polymer and Carbon Materials, Polish Academy of Sciences, ul. M. Curie-Sklodowskiej, 3441-800, Zabrze, Poland

    Barbara Robak, Barbara Trzebicka & Andrzej Dworak

Authors
  1. Natalia Toncheva-Moncheva
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  2. Philip Dimitrov
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  3. Christo B. Tsvetanov
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  4. Barbara Robak
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  5. Barbara Trzebicka
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  6. Andrzej Dworak
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  7. Stanislav Rangelov
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Correspondence to Stanislav Rangelov.

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Toncheva-Moncheva, N., Dimitrov, P., Tsvetanov, C.B. et al. Formation of mesoglobules in aqueous media from thermo-sensitive poly(ethoxytriethyleneglycol acrylate). Polym. Bull. 67, 1335–1346 (2011). https://doi.org/10.1007/s00289-011-0545-5

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  • DOI: https://doi.org/10.1007/s00289-011-0545-5

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