Surfactant formation efficiency of fluorocarbon-hydrocarbon oligomers in supercritical CO2

We use dissipative particle dynamics simulations to explore the phase behavior and solution properties of ABCBA type model surfactants in near-supercritical CO(2) environment. We present design guidelines for functional surfactants with tunable properties. The block co-oligomers used in this study are made up of a CO(2)-phobic block having ethyl propionate and nine different types of ethylene monomers, flanked on either side by eight repeat units of fluorinated CO(2)-philic blocks. The most promising design block co-oligomer in the series is that with the longest CO(2)-phobic group in the ethylene monomers. For this particular oligomer, we systematically analyze the effect of concentration on the self-assembly behavior. Spherical micelles form in the 5%-65% volume fraction range for this oligomer, with the highest number of spherical micelles occurring at 45% surfactant in CO(2). When the volume fraction of the surfactant is increased from 70% to 85%, cylindrical micelles occur. We further investigate the effect of the length of the solvophilic fluorinated segments on self-assembly and find that stable micelles occur in a window of 8-14 repeat units. We find that the most critical contribution to stability is due to the mixing free energy between the chain tails residing in the outer layers and the interpenetrating molecules.