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Solvent Methane Ethane Ethyne Hexafluoroethane Carbon dioxide n-hexane 118.3 Methanol 32.3 Acetone 63.3 1.4 Interactions of Carbon Dioxide with Polymers and Monomers 9 Fig. 1.8 Charge distributions for various molecular interactions. alignment of directional interactions as dipoles or quadrupoles is disrupted by the thermal energy, leading to a nonpolar behavior. Hence, it may be possible to dissolve a nonpolar solute or a polymer in a polar supercritical fluid. However, to obtain sufficient density for dissolving the solutes at these elevated tempera- tures, substantially higher pressures need to be applied. Additionally, specific in- teractions such as complex formation and hydrogen bonding can increase the solvent strength of the supercritical fluid. These interactions are also highly temperature sensitive. The solvent strength of carbon dioxide for solutes is dominated by low polar- izability and a strong quadrupole moment (Table 1.3). Consequently, carbon di- oxide is difficult to compare to conventional solvents because of this ambivalent character. With its low polarizability and nonpolarity, carbon dioxide is similar to perfluoromethane, perfluoroethane, and methane. In general, carbon dioxide is a reasonable solvent for small molecules, both polar and nonpolar. With the exception of water, for many compounds, includ- ing most common monomers, complete miscibility can be obtained at elevated pressures. However, the critical point of the mixture, i.e. the lowest pressure at a given temperature where CO2 is still completely miscible, rises sharply with increasing molecule size. Consequently, most larger components and polymers exhibit very limited solubility in carbon dioxide. Polymers that do exhibit high solubility in carbon dioxide are typically characterized by a flexible backbone and high free volume (hence a low glass transition temperature Tg), weak inter- actions between the polymer segments, and a weakly basic interaction site such Table 1.3 Physical properties of various solvents [48–50], where a is the polarizability, l is the dipole moment and Q is the quadrupole moment. a·1025 (cm3) 26 l (D) 0.0 0.0 0.0 0.0 0.0 0.0 1.7 2.9 Q ́ 1026 (erg1/2cm5/2) –0.7 +3.0 –0.7 –4.3 45.0 33.3 47.6 27.6PDF Image | Supercritical Carbon Dioxide for Sustainable Polymer Processes
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