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10 1 Supercritical Carbon Dioxide for Sustainable Polymer Processes Fig. 1.9 Polymeric structures soluble in scCO2. (a) Perfluoropoly(propylene oxide), (b) polydimethylsiloxane, (c) poly(ethylene, propylene and butylene oxide), (d) polyvinylacetate, (e) poly(ether carbonate). as a carbonyl group [51–54]. Carbon dioxide-soluble polymers incorporating these characteristics include, e.g., polyalkene oxides, perfluorinated polypropy- lene oxide, polymethyl acrylate, polyvinyl acetate, polyalkyl siloxanes, and poly- ether carbonate (Fig. 1.9). Although the solubility of polymers in CO2 is typically very low, the solubility of carbon dioxide in many polymers is substantial. The sorption of carbon dioxide by the polymers and the resulting swelling of the polymer influence the mechanical and physical properties of the polymer. The most important effect is plasticization, i.e. the reduction of the Tg of glassy polymers. The plasticization effect, character- ized by increased segmental and chain mobility as well as an increase in inter- chain distance, is largely determined by polymer-solvent interactions and solvent size [55]. The molecular weight of the polymer is of little influence on the swelling once the entanglement molecular weight has been exceeded. The interaction of CO2 and polymers can be divided into three application areas: processing of swollen or dissolved polymers and applications where car- bon dioxide does not interact with the polymer. An extensive review on polymer processing using supercritical fluids has been written by Kazarian [55], includ- ing possible applications based on the specific interaction of CO2 and the poly- mer system involved. Obviously, the sorption and swelling of polymers by CO2 are crucial effects in designing polymer processes based on high-pressure technology, because impor- tant properties such as diffusivity, viscosity, glass transition, melting point, com- pressibility, and expansion will change. The plasticization effect of CO2 facili- tates mass transfer properties of solutes into and out of the polymer phase, which leads to many applications: increased monomer diffusion for polymer synthesis, enhanced diffusion of small components in polymers for impregna- tion and extraction purposes, polymer fractionation, and polymer extrusion.PDF Image | Supercritical Carbon Dioxide for Sustainable Polymer Processes
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