Thermodynamics and Kinetic Processes of Polymer Blends and Block Copolymers in the Presence of Pressurized Carbon Dioxide

Environmentally‐responsible materials processing is becoming an important global consideration in a wide variety of technologies, especially those wherein volatile and/or residual organic solvents cannot be tolerated. In this context, polymer processing has benefited tremendously from advances achieved using high‐pressure CO₂ as a viscosity modifier, plasticizing agent, foaming agent, and reaction medium. Pressurized CO₂ is environmentally benign, inexpensive, sustainable, and versatile owing to its gas‐like viscosity and liquid‐like solubility, which can be tuned through judicious choice of temperature and pressure. The addition of high‐pressure CO₂ to homopolymer blends and block copolymers can have a profound impact on polymer thermodynamics and kinetic processes since the number of interacting species increases. As a result, the compressibility as well as plasticization and intermolecular screening effects become non‐negligible. In this work, we review how these factors influence such polymeric systems, and discuss commercial polymer processes and applications that benefit from the use of high‐pressure CO₂.