Copolymerization of fluorinated monomers: recent developments and future trends

This review summarizes several aspects of the copolymerization of fluoroalkenes with nonhalogenated or fluorinated olefins. According to the amounts of monomers involved, the resulting polymers may fall into various kinds of materials: thermoplastics, elastomers and thermoplastic elastomers. Hence, novel polymers are produced with complementary properties due to functional groups (e.g., solubility, adhesion, curing). In addition, this survey shows how a wide variety of monomers, reactive in copolymerization with fluoroolefins, lead to new products. In most cases, random copolymers are obtained. Regarding the kinetic and basic points of view, the Q and e parameters (linked to the reactivity) of most fluoroalkenes are supplied. Further, the structure of the copolymers is also discussed taking into account theoretical and thermodynamic concepts. Finally, alternating copolymerization based on electron-withdrawing fluorinated monomer with electron-donating hydrogenated comonomer (e.g., vinyl ethers) is presented and illustrated with examples.