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CARBON DIOXIDE TECHNOLOGY PLATFORM 123 the way for transferring this technology to full-scale plant operations (13). Con- struction has begun on a new DuPont facility to test production of fluoropolymers in carbon dioxide. The $40 million plant will be located in Bladen County, North Carolina and is scheduled to be completed by 2006. If the test facility is successful, DuPont is scheduled to expand the Bladen County facility, investing up to $275 million over the next 7 years. 2.2 CO2-Philic/Hydrophilic Surfactants In addition to amorphous low-melting fluoropolymers and siloxane-based poly- mers, carbon dioxide is a good solvent for high vapor pressure fluids. Although it readily dissolves many of these small molecules, CO2, in both the liquid and supercritical states, is a very poor solvent for many compounds, including most high molecular weight polymers and polar compounds such as water, ionic species, proteins, etc. In order for CO2 to be an effective continuous phase for applications such as separations, extractions, coatings, and polymerizations, surfactants must be developed analogous to classical surfactant systems in conventional continuous phases (i.e. water or inverse systems). However, unlike conventional organic solvents that are often capable of dis- solving high molar mass oleophilic compounds [e.g. the ability to readily dissolve poly(propylene oxide), polyisoprene, polybutadiene, and polystyrene in solvents such as toluene, cyclohexane, and tetrahydrofuran], CO2 is a poor solvent for most of these compounds at readily accessible conditions (<300◦C and <350 bar). Indeed, CO2 is more akin to a fluorinated solvent (fluorous phase) than it is to hydrocarbon solvents. As such, we can classify (14) the solubility charac- teristics from a CO2-centric viewpoint whereby we can have compounds that can be classified as “CO2-philic” and “CO2-phobic.” CO2-phobic compounds can be further subdivided into hydrophilic and lipophilic or oleophilic (Figure 7). With this being understood, one can now molecularly engineer interfacially active com- pounds through the judicious catenation of CO2-philic segments with CO2-phobic segments. DeSimone (9, 14–17), Fulton (17, 18), Johnston (19, 20), and Beckman (21, 22) have established the design criteria for molecularly engineered surfactants that can stabilize and disperse otherwise insoluble matter into a CO2 continuous phase. Through their research efforts, an ideal model surfactant for CO2 contains a CO2- philic segment that is comprised of either a fluorinated segment or a siloxane segment attached to a CO2-phobic segment of oleophilic or hydrophilic character (22a,b). By altering the molecular weight, morphology, topology, composition, temperature, and pressure, amphilies of this nature enhance the efficacy of liquid and supercritical CO2 to dissolve or emulsify highly polar and highly lipophilic, oligomeric, and polymeric compounds. 2.2.1 Graft Copolymer Surfactants for CO2 Applications A copolymer of poly (ethylene oxide) (PEO) grafted onto a backbone of poly(1,1-dihydroperfluorocylPDF Image | OPPORTUNITIES FOR POLLUTION PREVENTION
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