Synthesis, Structure, and Surface Properties of Poly(meth)acrylates Bearing a Vinylene-Bridged Fluoroalkyl Side Chain

Abstract In this study, unprecedented polyacrylates with vinylene-bridged fluoroalkyl side chains (-(CF2)6-CH=CH-(CF2)5CF3) were successfully synthesized. These polyacrylates comprise short perfluoroalkyl groups, thus allowing to prevent the formation of bioaccumulative polyfluorinated compounds including perfluorooctanoic acid (PFOA). The bulk organization and surface properties of these polymers were investigated by differential scanning calorimetry, X-ray diffraction analysis, and contact angle measurements. Thin films of the novel polyacrylates bearing the -(CF2)6-CH=CH-(CF2)5CF3 groups exhibited excellent water and oil repellency comparable to those made by conventional polyacrylates bearing C8F17 groups. A novel polymethacrylate bearing the -(CF2)6-CH=CH-(CF2)5CF3 group showed low surface energy and low contact angle hysteresis despite of its amorphousness in the bulk state, which is very different from conventional polymethacrylates bearing a C6F13 group. Therefore, these polyacrylates bearing vinylene-bridged fluoroalkyl side chains are promising alternatives to conventional analogues containing long perfluoroalkyl side chains.