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120 TAYLOR CARBONELL DESIMONE 2. implications for reaction kinetics) and liquidlike densities that allow for solva- tion of many compounds. Small changes in temperature or pressure enable CO2 to exhibit changes in solvent density without altering solvent composition (2). In addition, the low viscosity of supercritical CO2 and its ability to plasticize glassy polymers have implications for polymer processing and kinetics. CO2 has an easily accessible critical point with a Tc of 31.1◦C and a Pc of 73.8 bar. Furthermore, CO2 is nontoxic and inexpensive ($0.05/lb). The dissolving power of CO2 is tunable over a broad range of solvent quality because of its compressibility, especially in the supercritical region (2–5) (Figure 5). As a naturally occurring gas, CO2 exists in natural reservoirs of high purity located throughout the world, including the Four Corners region where Utah, Colorado, New Mexico, and Arizona intersect (6). CO2 is also abundantly present in natural reservoirs in the Mississippi, where it is transported by pipeline to many west Texas oil fields for use in enhanced oil recovery processes (6). In addition, it is generated in large quantities as a byproduct in ammonia, hydrogen, and ethanol plants. Indeed, CO2 is as ubiquitous as water, yet it is much less precious. Electrical power generation stations that burn fossil fuels supply ∼90% of the world’s commercial energy and generate copious amounts of CO2 (7). In fact, since the industrial revolution, there has been a significant increase in the amount of CO2 (a green house gas) emissions. It is estimated that less than 1% of the CO2 that is generated is captured for use, hence the demand for CO2 will always be far less than what is generated as a by-product. ENABLING EARLY DEVELOPMENTS Technological breakthroughs in the last decade indicate that dense carbon diox- ide could be the most commonly used solvent in the twenty-first century (8). A major incentive for using CO2 as a solvent for commercial polymerizations is the elimination of environmentally harmful organic solvents and reduction of waste streams generated during polymerizations. There is also the potential to lower residual monomer levels by online supercritical fluid extractions. Polymers can be produced in dry form with no solvent or water-drying step. This affords significant energy savings by the elimination of the heat of vaporization of water needed to dry polymers produced by traditional aqueous emulsion, suspension, and solu- tion polymerizations. Polymer processing energy requirements are also reduced by utilizing downstream CO2-based operations (i.e. polymer extrusion). It is clear from all of the reasons outlined above that CO2 would be an ideal emerging technology platform to mitigate or even eliminate many of the problems associated with conventional solvents. However, two significant barriers inhibit this vision: the poor solvency of CO2 (hence the need to design surfactants for CO2) and the lack of understanding regarding the usefulness of CO2 as a reac- tion medium. Two recent developments—the synthesis of fluoropolymers in CO2 (including the discovery of the high solubility of many fluoropolymers in CO2)PDF Image | OPPORTUNITIES FOR POLLUTION PREVENTION
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