Aggregation of Amphiphilic Molecules in Supercritical Carbon Dioxide: A Small Angle X-ray Scattering Study

Abstract

Highly soluble amphiphilic materials are shown to form aggregates in supercritical CO{sub 2}. The strategy for synthesis of these amphiphilic molecules involves incorporating CO{sub 2}-philic segments that, for this study, are perfluorinated alkyl chains. These CO{sub 2} -philic regions function like the hydrocarbon tails of conventional surfactant molecules used in liquid organic solvents. Synthesis and characterization of three different CO{sub 2} amphiphiles are reported. Subsequent small angle X-ray scattering (SAXS) measurements were used to characterize the aggregation of these materials in supercritical CO{sub 2}. Each of the three amphiphiles studied showed a different type of aggregation behavior. A graft copolymer consisting of a CO{sub 2}-philic backbone and CO{sub 2}-phobic grafts associated into a micellar structure in the presence of water to promote hydrogen bonding. These aggregates contain approximately 600 grafts in the core. The commercially available surfactant perfluoroalkylpoly( ethylene oxide), or F(CF{sub 2}){sub 6-10}CH{sub 2} CH{sub 2}O(CH{sub 2}CH{sub 2}O){sub 3-8}H, forms classic reverse micelle structures having radii of about 84 A under the conditions of high pressure required to solubilize the material. A third amphiphile, the semifluorinated alkane diblock molecule F(CF{sub 2}){sub 10}(CH{sub 2}){sub 10}H, may form small aggregates of at most 4 unimers per aggregate. 41 refs., 10 figs.,more » 1 tab.« less