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124 TAYLOR CARBONELL DESIMONE Figure 7 Solubility of polymers in carbon dioxide. acrylate) (PFOA) or PFOA-g-PEO has been synthesized by Maury et al (14). The PEO macromonomer was analyzed prior to grafting into the copolymer and determined by gel permeation chromatography to have a molecular weight of 5000 g/mol. The copolymer was characterized in Freon-113 by proton nuclear magnetic resonance spectroscopy to determine the percent PEO incorporation. The final graft copolymer was found to contain 15% ethylene oxide based on the total weight of the polymer. The graft copolymer was reported to have a low solubility in conventional solvents, making characterization difficult, yet interesting results were obtained when solution properties in CO2 were studied with the aid of small angle X-ray scattering measurements (17). The scattering measurements were observed in CO2 at 60◦C in the presence of water (water-to-surfactant ratio of 0.32). A 5000 PEO segment is completely insoluble in CO2, and this fact, coupled with the scattering data, led the authors to a model in which the PEO grafts exist in the center of a core-shelled structure (17). The PFOA-based shell limits the CO2-PEO interaction, thus facilitating the stabilization of a micellar structure. The radius of the PEO core wasdeterminedtobe105A ̊,adiametermuchlargerthanasingle,collapsed5K PEO chain. This led to the conclusion that the PEO chains attached to a single PFOA backbone as well as those from other graft copolymer chains aggregate in the core region of the micelle. Approximately 600 PEO segments occupy the core, based on the measured volume of the micelle core and the bulk density of PEO. The micellelike structure of the graft copolymer solution greatly enhanced the solubility of water in the CO2 solvent. Up to 10 wt% of the copolymer was soluble in CO2 at 220 bar and 60◦C. 2.2.2 Block Copolymer Surfactants for CO2 Applications A small diblock molecule consisting of a perfluoroalkane chain has been covalently linked to aPDF Image | OPPORTUNITIES FOR POLLUTION PREVENTION
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