Thermodynamics and kinetics on micelle formation of a nonamphiphilic poly(vinylphenol)-block-polystyrene by α,ω-diamine View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2005-10

AUTHORS

Eri Yoshida, Shinichi Itsuno

ABSTRACT

A poly(vinylphenol)-block-polystyrene diblock copolymer (PVPh-b-PSt) forms micelles in the presence of 1,4-butanediamine (BDA) in 1,4-dioxane, a nonselective solvent. The micellization proceeds through the formation of hydrogen bond cross-linking between the PVPh blocks via BDA, and the dissociation and reconstruction of the micelles is reversibly controlled by temperature. We explored the thermodynamics and kinetics on the micellization of the nonamphiphilic PVPh-b-PSt copolymer by BDA. Light scattering studies demonstrated that an equilibrium existed between the micelles and the unimers. The equilibrium constants were determined for the dissociation and the reconstruction of the micelles on the basis of variation in the aggregation number of the micelles. The equilibrium constant of the dissociation showed a good agreement with the reciprocal of the equilibrium constant of the reconstruction. Based on the equilibrium constants, the standard Gibbs energy, enthalpy, and entropy of the dissociation and reconstruction were estimated. The standard enthalpy was Δ H° = 30–40 kJ mol−1 for the dissociation. The enthalpy of the reconstruction was obtained as a negative value, however, there was a negligible difference in the absolute values of Δ H° between the dissociation and the reconstruction. The rate constant of the micellization was ca. 102 times larger than the back reaction, and increased with a decrease in the temperature. More... »

PAGES

19-25

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/s00396-005-1325-2

DOI

http://dx.doi.org/10.1007/s00396-005-1325-2

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