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Thermodynamic and kinetic analysis of phase separation of temperature-sensitive poly(vinyl methyl ether) in the presence of hydrophobic tert-butyl alcohol

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Abstract

NMR and isothermal titration calorimetry (ITC) techniques were chosen to examine interactions in a poly(vinyl methyl ether) (PVME)/tert-butyl alcohol (t-BuOH)/water ternary system. The effects of PVME and t-BuOH concentrations on phase separation temperature were examined. Molecules of t-BuOH additive hydrophobically associate with PVME and decrease the phase separation temperature. Thermodynamic parameters connected with phase separation were calculated from NMR results using an approach based on the van’t Hoff equation. Presence of t-BuOH increases the number of PVME monomeric units in one cooperative domain (where the units undergo phase separation as whole—‘all-or-none’). NMR time-resolved relaxation measurements show very different dynamics of the solvent releasing process for low and high PVME concentrations above phase separation temperature. ITC data show that the presence of t-BuOH restricts water solvation of PVME globules. Presented results on the PVME/t-BuOH/D2O system show that the PVME solution properties are not constant in time. The analysis of measurements (and resulting properties) should always be done while considering strong time-dependent behaviour of PVME solutions.

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Acknowledgements

This work was supported by the World Premier International Research Initiative (WPI Initiative), Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan and the Grant Agency of the Academy of Science of the Czech Republic (Grant No. 15-10527 J). The authors also acknowledge the Charles University, Prague for the opportunity for N. Velychkivska’s doctoral studies.

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Authors and Affiliations

  1. Institute of Macromolecular Chemistry, AS CR, Heyrovsky Sq. 2, 162 06, Prague, Czech Republic

    Nadiia Velychkivska, Anna Bogomolova, Sergey K. Filippov & Larisa Starovoytova

  2. International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan

    Jan Labuta

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  1. Nadiia Velychkivska
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  2. Anna Bogomolova
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  3. Sergey K. Filippov
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  4. Larisa Starovoytova
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  5. Jan Labuta
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Correspondence to Jan Labuta.

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Velychkivska, N., Bogomolova, A., Filippov, S.K. et al. Thermodynamic and kinetic analysis of phase separation of temperature-sensitive poly(vinyl methyl ether) in the presence of hydrophobic tert-butyl alcohol. Colloid Polym Sci 295, 1419–1428 (2017). https://doi.org/10.1007/s00396-017-4100-2

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  • DOI: https://doi.org/10.1007/s00396-017-4100-2

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