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SYNOPSISIt has been found that carbon dioxide remarkably accelerates the absorption of many low molecular weight additives into a number of glassy polymers. This effect is due to the high diffusivity, solubility, and plasticizing action of compressed COP in polymers. The transport of CO, and the effects of CO, pressure on the transport of other low molecular weight compounds in polymers have been studied by a simple gravimetric method Polymer film samples were contacted in a pressure vessel with compressed CO,, or with COP plus various organic liquids or solids, and the sample weight was followed with a fast-response electronic balance during subsequent desorption at atmospheric pressure. Upon release of the pressure, absorbed CO, rapidly diffuses from the polymer, while the other compounds desorb much more slowly. The amount of additive absorbed can be determined from the plateau weight of the sample after most of the CO, has escaped. Extensive kinetic and equilibrium data are reported for the model system poly (vinyl chloride)/dimethyl phthalate/CO,, and a number of other examples of C0,-assisted additive absorption are given. This "infusion" process, in effect, amounts to the partitioning of the additive between the COz-and polymerrich phases; consequently, the relative solubility of the additive in CO, and in the polymer is a major factor governing the amount of additive absorbed. Data reported here illustrate the generality and potentially broad applicability of C0,-assisted polymer impregnation.

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A mathematical model was developed to describe diffusion of a penetrant and a solute in a swellable polymer slab. The model was applied to the case of a hydrophilic polymer loaded with a soluble bioactive agent, in which the penetrant (water) is sorbed and solute is desorbed. The model allows the incorporation of any appropriate form of the diffusion coefficients. A Fujita‐type exponential dependence on penetrant concentration was chosen and shown to be adequate for prediction of a range of transport behavior. Dimensional changes in the sample were predicted by allowing each spatial increment to expand according to the amount of penetrant sorbed. During the initial period of release, the swelling was restricted to one dimension by the glassy core of the sample. At a later point in the process, the center of the sample had sorbed enough penetrant to plasticize it, and the sample relaxed to an isotropically swollen state; thereafter swelling was three‐dimensional.

A mathematical model developed to describe diffusion of a penetrant and a solute in a swellable polymer slab was applied to the case of a hydrophilic polymer loaded with a soluble drug in which the penetrant (water) is sorbed and solute (drug) is desorbed. An exponential dependence of the penetrant and solute diffusion coefficients on penetrant concentration was chosen and shown to be adequate for description of the systems studied. Experimental verification of the model was conducted by using copolymers of 2‐hydroxyethyl methacrylate (HEMA) and N‐vinyl‐2‐pyrrolidone (NVP). The monomers were bulk polymerized with benzoyl peroxide initiator and cut into thin disks. Monomer mole fractions of HEMA in the copolymers were 0.707, 0.446, and 0.211. Swelling behavior of the samples was observed in water at 37 and 0°C. Solute‐containing samples were prepared and solute release from these samples into water was followed by monitoring the UV absorption of the release medium. The concentration dependence of the diffusivity of water and two model solutes, sodium trifluoroacetate and sodium heptafluorobutyrate, in the gels was studied by using the pulsed‐gradient spin‐echo NMR technique. The diffusivities measured by this technique followed the concentration dependence predicted by the free‐volume theory. The simple exponential dependence used in the model was an adequate approximation of this behavior in the case of a transient diffusion experiment.