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544 Chemical Reviews, 1999, Vol. 99, No. 2 Kendall et al. Jonathan Kendall was born in Charlotte, NC, in 1969. He received his B.S. in chemistry from the University of North Carolina at Chapel Hill in 1991. He received his Ph.D. in chemistry from Stanford University in 1997, under the direction of Professor James P. Collman. During graduate school, he synthesized bis(porphyrin) sandwich complexes for three materials applications: nonlinear optics, liquid crystals, and semiconducting charge- transfer materials. He then returned to Chapel Hill for postdoctoral research in Professor Joseph DeSimone’s lab. His work on polymer synthesis in liquid and supercritical carbon dioxide has been performed while serving as the Technical Coordinator for the Kenan Center for the Utilization of Carbon Dioxide in Manufacturing, a CO2-based research center sponsored by UNCsCH and North Carolina State University. Dorian Canelas was born in 1970 in Honolulu, HI and raised in Wheat Ridge, CO. She received a B.S. in chemistry from Northeastern University in 1993. As an undergraduate, she worked on step-growth polymerizations and membrane modification under the direction of L. F. Hancock at W.R. Grace. She earned a Ph.D. from the University of North Carolina at Chapel Hill in 1997 under the direction of J. M. DeSimone. Her graduate work focused on dispersion polymerizations of vinyl monomers in surfactant- modified supercritical carbon dioxide. She is currently working on new thermoset chemistry at Lord Corporation in Cary, NC. While the parameters that govern solubility of polymers in CO2 are not fully understood, several studies have been performed to probe the nature of solute-solvent interactions between polymers and CO2. CO2 has a low dielectric constant compared to alkanes, and its polarizability and polarizability/ volume are lower than ethane and propane.13 Al- though CO2 lacks a dipole moment, a substantial contribution to its solubility parameter is due to a large quadrupole moment. The quadrupole moment coupled with its Lewis acidity allow CO2 to partici- pate in interactions absent in hydrocarbons. Early work in this area suggested that weak interactions exist between CO2 and functional groups on the polymer chains such as sulfones14 and carbonyls.15 Later, systematic studies implied that the interac- Jennifer Young was born and raised in Timonium, MD. She earned her B.S. degree in chemistry from the University of Richmond in 1995. She is currently working toward her Ph.D. under the direction of Professor M. DeSimone at the University of North Carolina at Chapel Hill. Her studies are focused on dispersion polymerizations in liquid and supercritical carbon dioxide. Joseph DeSimone is Mary Ann Smith Professor of Chemistry at the University of North Carolina at Chapel Hill and of Chemical Engineering at North Carolina State University. He received his B.S. degree in chemistry in 1986 from Ursinus College in Collegeville, PA, and his Ph.D. in 1990 from the Department of Chemistry at Virginia Polytechnic Institute and State University. At VPI he worked with Professor James McGrath in the area of living polymerizations to synthesize novel block and graft copolymers. At UNCsCH, his research efforts are focused on developing synthetic pathways for polymer synthesis and processing in liquid and supercritical carbon dioxide. His accomplishments include homogeneous and heterogeneous polymerizations in CO2. Recently, he has investigated the design and synthesis of surfactants for use in CO2 as stabilizers in dispersion polymerizations, delivery of materials, and extractions. In 1996, he cofounded MICELL Technologies, which has developed environmentally friendly CO2-based dry-cleaning and metal degreasing systems. In 1997, he and Professor Ruben Carbonell at NCSU started the Kenan Center for the Utilization of Carbon Dioxide in Manufacturing (at UNCsCH and NCSU) to facilitate research on CO2-based polymer synthesis and processing. Professor DeSimone was a 1993 Presidential Faculty Fellow and winner of the 1997 Presidential Green Chemistry Challenge Award. He is also the 1999 winner of the Carl S. Marvel Creative Polymer Chemistry Award. tions between CO2 and the silicone portion of the polymer backbone govern the high solubility of these types of polymers.16 Work involving the use of Fourier transform infrared spectroscopy reveals that CO2 exhibits Lewis acid-base type interactions with electron-donating functional groups of polymer chains such as the carbonyl group of poly(methyl methacryl- ate) (PMMA).17 McHugh found that in copolymers of ethylene and methyl acrylate, increasing the methyl acrylate content increased polymer solubility.18 It wasPDF Image | Polymerizations in Supercritical Carbon Dioxide
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