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The use of supercritical (SC) carbon dioxide to process various biodegradable/biocompatible polymers for pharmaceutical and medical applications has attracted a great interest in the last two decades. A number of SC-fluid based techniques where the SC-CO2 acts as solvent, antisolvent or plasticizer have been used to obtain drug delivery systems. The main drawback in using the SC-CO2 as a solvent is represented by the poor solubility of most pharmaceutical products in the dense gas. The CO2 is a non-polar molecule with low molecular weight, scarcely able to dissolve molecules with more or less pronounced polar characteristics (such as weak bases or acids), and hydrophilic polymers.<br />The knowledge of the phase behavior of CO2/polymer binary system is a necessary prerequisite, in order to properly design and develop a SC-CO2-based processes such as the production of drug loaded microparticles or monolithic matrices. In this respect, the solubility of the polymer in SC-CO2 and the study of the behavior of the polymer in the presence of CO2 (swelling, foaming, melting point, etc.) are the most important issues that should be addressed.