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Poly(hydroxyethyl methacrylate-co-methacrylic acid) hydrogels can swell extensively in a high-pH medium where the carboxyl groups are ionized. The swelling equilibrium is a strong function of the methacrylic acid composition of the polymer and pH of the medium. The nonionized gel structure was found to be rather insensitive to the amount of cross-linker, tetraethylene glycol dimethacrylate (TEGDMA), incorporated, within the range of 0.5 to 3%. This result is supportive of the existence of secondary interactions that shield the effect of covalent cross-links. Phenylpropanolamine (PPA) was used as a probe solute to study the diffusion characteristics of the poly(HEMA-co-MA) gels. Its diffusion coefficient in the swollen matrices of different methacrylic acid compositions at various pH's was measured via a desorption method. It is evident that these diffusion coefficients follow Yasuda's free volume theory, which expresses an exponential relationship between the solute diffusivity in a swollen polymer membrane and the reciprocal of the membrane hydration. Although interactions exist between PPA and the hydrogel matrix, these interactions are not significant enough to perturb the free volume relationship established. This observation can be explained by the high ionic strength of the system.

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Drug release from a swelling hydrogel matrix is a complicated process where diffusion of drug molecules is coupled to the swelling kinetics. The swelling influences the diffusional flux of drug molecules by increasing the diffusion coefficient and diffusional pathlength. Release of phenylpropanolamine from apoly(hydroxyethy1 methacrylate-co-methacrylic acid) hydrogel, initially at low pH, is highly influenced by swelling in a neutral pH medium. Swelling in these ionizing gels is a very long process, even in the absence of a glassy core, indicating that the swelling is not a simple Fickian process. In this paper, a novel approach is introduced to model the phenylpropanolamine release from these swelling gels. Through a free volume relationship, the experimentally determined swelling kinetics are coupled to a diffusion mechanism for the drug molecules. This model was shown to give an accurate prediction of phenylpropanolamine release from poly(hydroxyethy1 methacrylate-co-methacrylic acid) gels.

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