Phase Equilibria of Binary and Ternary Mixtures with Poly(styrene-Co-hexafluorobutyl Methacrylate) and Solvents at High Pressure and Temperature

This paper presents the synthesis of the fluoric copolymer poly(styrene-co-2,2,3,4,4,4-hexafluorobutyl methac-rylate) [P(styrene-co-HFBMA)] through dispersed phase polymerization in a supercritical carbon dioxide (sc-CO2) medium. The physiochemical characteristics of P(styrene-co-HFBMA) were extensively studied by varying the styrene to HFBMA mole ratios (40:1, 25:1, and 20:1) and 2,2'-Azobisisobutyronitrile (AIBN) initiator at different mass percentages (mass%) from 1 to 4, along with the mean molecular mass (Mm). Phase transition data were reported for two-component and three-component P(styrene-co-HFBMA) in sc-C3H8, C3H6, C4H10, and C4H8, encompassing temperature "T" and pressure "P" limits (-341 to-459) K, and (-21 to-185) MPa, respectively. The phase behavior of the P(styrene-co-HFBMA) + solvent mixtures displayed an upper critical solution temperature (UCST) type behavior with a declining gradient. Equilibria curves were measured for the P (styrene-co-HFBMA) + (C3H10/C3H6) + CH3OCH3(i.e., DME) (25:1, AIBN mass%: 2.0) system in "P-T" phase diagram, spanning from the UCST region to LCST region at DME mass% ranging from 0.0 to 68.5. Additionally, solubility curves at "P": up to-148 MPa and "T": from-450 K to-350 K showed a shift from a declining slope to an inclined slope within the 0.0 to 60.3 mass% range for the P(styrene-co-HFBMA) (mole ratio:25:1; AIBN mass%: 2.0) + (C4H10/C4H8) + DME system. These findings provide valuable insights into the phase behavior and solubility characteristics of the P(styrene-co-HFBMA) copolymer in different sc-solvent mixtures.