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SynopsisThe Sanchez-Lacombe equation of state was used to model the sorption of high-pressure gases into solid, amorphous polymers and molten polymers. Only one adjustable parameter per binary pair, a,,, was used in the mixing rules to correct the deviation of the characteristic pressure of the mixture, PG, from the geometric mean. The values of S,, which gave the best fit of the available literature data for the carbon dioxide-polymethyl methacrylate, carbon dioxide-silicone rubber, ethylene-low density polyethylene, methane-polyisobutylene, methane-low-density and highdensity polyethylene, and methane-polystyrene systems ranged from -0.019 to 0.136. In all cases, the calculated sorption isotherms were in reasonably good agreement with the experimental data. The resultant swelling of polymethyl methacrylate and silicone rubber was also well represented by the Sanchez-Lacombe equation of state. Because the Sanchez-Lacombe theory is based on latticefluid theory, the sorption calculations are limited to polymers which are noncrystalline, not cross-linked or slightly crosslinked, above their glass transition temperature, or above their melting temperature. The sorption data for the amorphous polymers considered in this study were either at temperatures above the glass transition temperature of the polymer or were at sufficiently high pressures that the temperature was above the effective glass transition temperature as predicted from a theoretical relation presented by Chow.

Cloud‐point data to 180°C and 2800 bar are presented for polyethylene, poly(methyl acrylate), and two poly(ethylene‐co‐methyl acrylate) copolymers (10 and 31 mol % methyl acrylate) in propane and chlorodifluoromethane with two cosolvents, acetone and ethanol. The addition of small amounts of either cosolvent to the copolymer–solvent mixtures shifts the cloud‐point curve to lower pressures and temperatures, as both cosolvents provide favorable polar interactions with the acrylate group in the backbone of the copolymer. Ethanol has a larger effect than acetone since ethanol hydrogen bonds to the acrylate group. However, if the concentration of ethanol is increased above ca. 10 wt %, it self‐associates and reverts to antisolvent behavior, forcing the copolymer out of solution. For nonpolar polyethylene–propane mixtures, the polar cosolvents behave as traditional an‐tisolvents. In poly(methyl acrylate)–chlorodifluoromethane mixtures, both polar cosolvents enlarge the single‐phase region. The cloud‐point curves for the (co)polymer–propane–acetone mixtures are modeled reasonably well using the Sanchez–Lacombe equation of state with two adjustable mixture parameters. No attempt is made to model the mixtures that exhibit hydrogen bonding. © 1993 John Wiley & Sons, Inc.

Cloud‐point data to 180°C and 2,800 bar are presented for three poly(ethylene‐co‐methyl acrylate) copolymers [10, 31, and 41 mol % methyl acrylate (MA)] and for polyethylene in ethylene, ethane, propylene, and propane. At low concentrations of MA in the backbone of the copolymer, the saturated hydrocarbons are better solvents for the copolymer than their olefinic analogs because polarizability drives the phase behavior. For the higher MA‐content copolymers, which have more polar repeat units, the unsaturated hydrocarbons are better solvents owing to favorable quadrupolar interactions between the solvent and the polymer segments. The cloud‐point curves of the high MA‐content copolymers in the unsaturated hydrocarbons are shifted to very high temperatures to overcome strong acrylate‐acrylate interactions in the polymer. In fact, the 41 mol % MA copolymer cannot be dissolved in propane at temperatures to 180°C and pressures to 2,800 bar even though the copolymer is predominantly ethylene, while the same copolymer dissolves in propylene at 40°C and at pressures as low as 1,400 bar. Although the Sanchez‐Lacombe equation of state is used to model the cloud‐point curves, two temperature‐dependent mixture parameters are needed for a good fit of the data. © 1992 John Wiley & Sons, Inc.

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