Cloud-point data to temperatures of 270 °C and 3000 bar are presented for CO2 with the family of poly(acrylates) including methyl, ethyl, propyl, butyl, ethylhexyl, and octadecyl, with poly(butyl methacrylate), with poly(vinyl acetate), with statistically random copolymers of poly(ethylene-co-methyl acrylate) with 41, 31, and 18 mol % acrylate, with poly(tetrafluoroethylene-co-hexafluoropropylene) and poly(vinylidene-co-hexafluoropropylene) copolymers, each with ∼20 mol % hexafluoropropylene, and with Teflon AF. Over the same range of conditions, CO2 cannot dissolve polyethylene, poly(acrylic acid), poly(methyl methacrylate), poly(ethyl methacrylate), polystyrene, poly(vinyl fluoride), or poly(vinylidene fluoride). CO2 is a weak solvent that exhibits the temperature-sensitive characteristics observed with polar solvents. The solubility of a nonpolar hydrocarbon polymer or a copolymer in CO2 can be increased by at least partially fluorinating the polymer or by incorporating some polar groups into the backbone architecture of the polymer. Because it is such a weak solvent, CO2 can distinguish differences in polymer architecture even for polymers from the same chemical family, which means that polymer free volume plays a role in determining solubility.
Phase behavior and small-angle neutron scattering (SANS) measurements are reported for poly(ethylene-co-1-butene) (PEB) dissolved in pentane, pentane plus ethane, and supercritical ethane to pressures of 2000 bar and temperatures of 130 and 150 °C. The solution microstructure and solvent quality are probed using the high-concentration isotopic labeling technique at the mixture critical concentration to determine the variation of intra-and intermolecular correlations on approach to the phase boundary with isothermal changes in pressure. The SANS results for the three solutions show that the intramolecular radius of gyration remains close to the unperturbed value over the entire pressure range investigated. However, the intermolecular correlation length changes dramatically as the phase boundary is approached and is approximately 3 times larger in ethane as compared to pentane even at 1000 bar from the phase boundary. The intermolecular correlation length data suggest that ethane is a poorer quality solvent than pentane at conditions close to the phase boundary even though both solvents have similar mass densities.
The cloud‐point behaviors of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐co‐22 mol % hexafluoropropylene) (VDF–HFP22) are reported at temperatures up to 250 °C and pressures up to 3000 bar in supercritical CO2, CHF3, CH2F2, CHClF2, CClF3, CH3CHF2, CH2FCF3, CHF2CF3, and CH3CClF2. The molecular weight of PVDF has a smaller effect on the cloud point than the solvent quality. Cloud‐point pressures for both fluoropolymers decrease as the solvent polarizability, polar moment per molar volume, and density increases. However, it is extremely difficult to dissolve either fluoropolymer in CClF3, which has a large polarizability and a small dipole moment. CO2 is an effective solvent because it complexes with the CF dipole at low temperatures where energetic interactions fix the phase behavior. In addition, polymer architecture has a strong impact on the cloud‐point pressure. VDF–HFP22 has lower cloud‐point pressures than PVDF in all solvents because it has a larger free volume that promotes facile interactions between the solvent and the polymer segments. Cloud‐point data are also reported for amorphous poly(tetrafluoroethylene‐co‐x mol % 2,2‐bistrifluoromethyl‐4,5‐difluoro‐1,3‐dioxole) (TFE–PDDx ; x = 65 and 85) in CO2. These data provide an interesting comparison to the PVDF–CO2 and VDF–HFP22–CO2 systems because TFE–PDD65 and TFE–PDD87 have very high glass‐transition temperatures of 160 and 240 °C, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2832–2840, 2000
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