Surfactant or block copolymer micelles ? Structural properties of a series of well-defined n-alkyl-PEO micelles in water studied by SANS

Here we present an extensive small-angle neutron scattering (SANS) structural characterization of micelles formed by poly(ethylene oxide)-mono-n-alkyl ethers (C-n-PEOx) in dilute aqueous solution. Chemically, C-n-PEOx can be considered as a hybrid between a low-molecular weight surfactant and an amphiphilic block copolymer. The present system, prepared through anionic polymerization techniques, is better defined than other commercially available polymers and allows a very precise and systematic testing of the theoretical predictions from thermodynamical models. The equilibrium micellar properties were elaborated by systematically varying the n-alkyl chain length (n) at constant PEO molecular weight or increasing the soluble block size (x), respectively. The structure was reminiscent of typical spherical starlike micelles i.e. a constant core density profile, similar to r(0), and a diffuse corona density profile, similar to r(-4/3). Through a careful quantitative analysis of the scattering data, it is found that the aggregation number, N-agg initially rapidly decreases with increasing PEO length until it becomes independent at higher PEO molecular weight as expected for star-like micelles. On the other hand, the dependency on the n-alkyl length is significantly stronger than that expected from the theories for star-like block copolymer micelles, N-agg similar to n(2) similar to what is expected for surfactant micelles. Hence the observed aggregation behavior suggests that the C-n-PEOx micelles exhibit a behavior that can be considered as a hybrid between low-molecular weight surfactant micelles and diblock copolymer micelles.