High-Pressure Phase Behavior for Poly[dodecyl methacrylate] + Supercritical Solvents + Cosolvents and Carbon Dioxide + Dodecyl Methacrylate Mixture

Abstract

Experimental cloud-point curves for poly(dodecyl methacrylate) [P(DDMA)] + dodecyl methacrylate (DDMA) or dimethyl ether (DME) in supercritical CO2 are reported for the binary and ternary mixtures up to 473 K and 248.0 MPa. The location of the P(DDMA) + CO2 cloud-point curve shifts to lower temperatures and pressures when DDMA or DME is used as a cosolvent. P(DDMA) does not dissolve in pure CO2 to the temperature of 493 K and the pressure of 260.0 MPa. High-pressure phase behavior data are presented for the CO2 + DDMA system at 313.2−393.2 K and up to ca. 25.2 MPa. The system exhibits type-I phase behavior with a continuous mixture-critical curve, and the system is adequately modeled with the Peng−Robinson equation of state. High-pressure phase behavior data are reported for P(DDMA) in supercritical propane, propylene, butane, and 1-butene. Cloud-point curves for the P(DDMA) in C4 hydrocarbons are at lower temperatures than the P(DDMA) + C3 hydrocarbons curves at fixed pressures.

Phase behavior for the poly(dimethylsiloxane) in supercritical fluid solvents

“…We are expected to obtain the phase behavior for polymer + supercritical solvents mixture using the high-pressure experimental apparatus [11]. The pressure inside cell is measured with a Heise gauge (Dresser Ind., USA, model CM-108952, 0 $345.0 MPa, accurate to within AE0.35 MPa) and high-pressure generator (HIP Inc., USA, model 37-5.75-60).…”

Molecular dynamics study on the dissolution behaviors of poly(vinyl acetate)‐polyether block copolymers in supercritical CO2

“…It is possible to increase the solubility of polymer in CO 2 by adjusting the interaction of CO 2 –CO 2 , that is, the cosolvents such as the monomers of the polymer and organic solvents could be used to change the interactions of CO 2 –CO 2 and polymer–CO 2. 13–15 In our previous work, the phase behaviors of PVAc + CO 2 + cosolvents ternary systems were investigated by experiment and the mechanism of cosolvents on the dissolution behaviors of PVAc in scCO 2 were discussed by the molecular dynamics simulations 16–18 . The cosolvents can provide favorable physicochemical interactions to increase the region of miscibility and reduce the free volume difference between the polymer and CO 2.…”

Phase Behavior for Poly(vinylacetate) + Carbon Dioxide + Cosolvent Ternary Systems

“…In general, polar cosolvents are used to enhance the solubility of polymer in CO 2 unless the cosolvents form a complex with the polar repeat units in the polymer . In previous works, the cosolvents in polymer + CO 2 mixtures were often the monomer of the polymer or organic solvent, the structural formula of which is similar to that of the monomer, such as styrene in polystyrene, n -butane in polyethylene, methyl methacrylate in poly­(methyl methacrylate), ethanol in poly­(ethylene glycol), ethylene in poly­(ethylene- co -vinyl acetate), decyl methacrylate in poly­(decyl acrylate), and dodecyl methacrylate in poly­(dodecyl methacrylate) . As the CO 2 -philic homopolymer, experimental data for the binary PVAc + CO 2 system has been reported elsewhere. ,,, However, reports regarding cosolvents that can enhance the solubility of PVAc in CO 2 are very few for any kinds of cosolvents …”