Cosolvent effects on the micellization of oxyphenyl(copoly)ethylene oxide copolymers in aqueous solution

In the present paper, we have analyzed how the presence of ethanol affects the micellization process of two structurally related polyoxyethylene block copolymers with diblock and triblock architectures (diblock, S15E63; triblock, E67S15E67) and the same hydrophobic block length, formed by oxyphenylethylene units, through surface tension, static and dynamic light scattering, density, ultrasound velocity, transmission electron microscopy, and steady-state fluorescence techniques. E and S denote the oxyethylene (-OCH2CH2) and oxyphenylethylene (-OCH2CH(C6H5)) units, respectively, and the subscripts the block length. The effect of increasing amounts of ethanol in solution gives rise to a progressive disruption of the micelle structures formed by these copolymers, with an increase in the critical micelle concentration (cmc) values and a decrease in the micellar aggregation number. This originated from the deswelling of the poly(ethylene oxide) (PEO) chains due to a decrease of the water content, accompanied by a reduction of the solvophobicity and an increase of the solubility of the S blocks, causing the lowering of the interfacial tension between the polyoxyphenylethylene core and the solvent, and favoring the swelling of hydrophobic blocks. Therefore, to achieve thermodynamic equilibrium, the micelle size should be smaller. A model derived from small angle neutron scattering (SANS) data is also applied to get extra information on micelle structure. With the aim of obtaining information about the hydration of micellar solutions of these block copolymers, compressibility and fluorescence data were collected. The increase of compressibility with ethanol addition confirms the swelling of the hydrophobic polyoxyphenylethylene chains. Fluorescence data show that the addition of ethanol to the solution decreases the polarity, favoring the solubilization of the oxyphenylethylene chains in the mixed solvent as single monomers. Aggregation data derived from this technique are in fair agreement with those obtained from light scattering.