Solubilization of Aromatic Hydrocarbons in Ethylene Oxide‐Propylene Oxide Triblock Micelles: Location of Solubilizate and its Effect on Micelle Size from 2D NMR and Scattering Techniques

Abstract

AbstractThe solubilization of benzene and toluene in micellar solutions and the effects on the micellization and micelle size of ethylene oxide‐propylene oxide triblock copolymers were investigated by dynamic light scattering (DLS), small angle neutron scattering (SANS), and 2D NMR spectroscopy. The copolymeric surfactants have the same size as the middle hydrophobic polypropylene oxide block (Mol. Wt. 3250) and varying polyethylene oxide end blocks (30, 40 and 50%). The solubilization and the properties of the micelles in the presence of the solubilizates were investigated; the results reveal that the more hydrophobic copolymer showed better solubilization. The cloud points of the copolymers decreased in the presence of oils; the depression in the cloud point is due to the formation of an electron donor–acceptor complex. DLS shows that the effect of benzene is dominated at high oil concentration. SANS data show that the micelles remain spherical in shape and that the micellar core size does not change with higher benzene concentration; observed changes in the low scattering vector region could be because of some small amount of benzene clusters formed at higher benzene concentration. Finally, the locus of solubilization of the oils in the copolymer micelles was determined via 2D NMR experiments. In all cases, significant nuclear Overhauser effect spectroscopy (NOESY) cross peaks were observed that appeared to correlate well with the expected loci of these solubilizates in micelles. Hence, the noninvasive NOESY technique provides important information on the location of the aromatic solubilizates in these copolymer micelles that depends on the structure of the oils.