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8 1 Supercritical Carbon Dioxide for Sustainable Polymer Processes Fig. 1.7 Schematic view of a catalytic polymerization based on CO2 technology, in which the catalyst and monomers can be recycled in a closed-loop process. from a process point of view. These include its relatively chemical inertness, readily accessible critical point, excellent wetting characteristics, low viscosity, and highly tunable solvent behavior, facilitating easy separation. The use of such a “volatile” solvent makes the solvent removal step relatively easy. In principle, this allows for a closed-loop polymer process, in which the components like cat- alyst and monomers can be recycled. Fig. 1.7 schematically illustrates the effi- ciency of a CO2-based polymerization as compared to a conventional process shown in Fig. 1.1. Moreover, supercritical carbon dioxide is a non-toxic and non-flammable sol- vent with a low viscosity and high diffusion rate and no surface tension. A drawback of CO2, however, is that only volatile or relatively non-polar com- pounds are soluble, as CO2 is non-polar and has low polarizability and a low di- electric constant, as discussed in Section 1.4. 1.4 Interactions of Carbon Dioxide with Polymers and Monomers For application of supercritical CO2 as a medium in polymer processes, it is im- portant to consider its interactions with polymers and monomers. In general, the thermodynamic properties of pure substances and mixtures of molecules are determined by intermolecular forces acting between the molecules or poly- mer segments. By examining these potentials between molecules in a mixture, insight into the solution behavior of the mixture can be obtained. The most commonly occurring interactions are dispersion, dipole-dipole, dipole-quadru- pole, and quadrupole-quadrupole (Fig. 1.8). For small molecules, the contribution of each interaction to the intermolecu- lar potential energy Cij (r,T) is given by the polarizability a, the dipole moment l, the quadruple moment Q, and in some cases specific interactions such as complex formation or hydrogen bonding [49]. The interactions work over differ- ent distances, with the longest range for dispersion and dipole interactions. Note that the dispersion interaction depends on the polarizability only and not on the temperature. Consequently, an increased polarizability of the supercriti- cal solvent is expected to decrease the pressures needed to dissolve a nonpolar solute or polymer. Furthermore, at elevated temperatures, the configurationalPDF Image | Supercritical Carbon Dioxide for Sustainable Polymer Processes
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