Polymerization of vinylidenefluoride (VF2) in a supercritical fluid medium

A process for reacting fluoroolefin to form a polymer, comprising the steps of:

• feeding solvent to a reactor vessel, the solvent being essentially non-reactive with the fluoroolefin and having a critical temperature less than a melting point of the polymer;
• supplying at least one fluoroolefin monomer to the reactor vessel so that at completion of the feeding and supplying steps total monomer concentration is at least twenty percent by weight of a monomer-carbon dioxide mixture;
• establishing reaction conditions inside the reactor vessel to provide a reactive state for a polymerization reaction such that temperature is above a critical temperature of the solvent and less than a melting point of a desired polymer product, and pressure ranges from 50 atm to 450 atm;
• introducing an initiator into the reactor vessel to form a reaction mixture;
• reacting the reaction mixture in the reactive state to effect free radical polymerization and form a polymer;
• and
• depressurizing the reactor vessel to recover the polymer.