Solution copolymerization of perfluoroalkyl ethyl methacrylate with methyl methacrylate and butyl acrylate: Synthesis and surface properties

•Random copolymers of Zonyl-TM, MMA and BA were synthesized with high conversions.•Low cost and less toxic toluene/methyl ethyl ketone mixture was used as solvent.•Zonyl-TM and BA decreased the glass transition temperature of copolymers.•Zonyl-TM and BA increased water and oil repellence of the copolymers considerably.•Small ratio of Zonyl-TM decreased surface free energy down to 9.7mJ/m2. Random copolymers of perfluoroalkyl ethyl methacrylate (Zonyl-TM), methyl methacrylate (MMA) and butyl acrylate (BA) monomers were synthesized by free radical copolymerization in toluene/methyl ethyl ketone solvent mixture. Batch polymerizations have been performed using different monomer feed compositions with high conversions. Molecular weights of the copolymers were determined by GPC and intrinsic viscosity measurements. Chemical structures of the copolymers were characterized by 1H-NMR and Tg values were determined by DSC. Thin films were prepared by dip coating glass slides into copolymer solutions and water and oil repellence, surface free energies were measured by contact angle measurement. Mainly, the effects of addition of BA and Zonyl-TM on the structure and surface properties of the copolymers were investigated. It was found that the Tg value of copolymers decreased considerably by the addition of Zonyl-TM and BA into the feed due to the internal plasticizing effects of both monomers. Water contact angles of the copolymers were increased from 71° to 119° with the increase of the Zonyl-TM content. Addition of BA was found to be more effective than MMA to introduce hydrophobicity onto the surface. Small amount of Zonyl-TM incorporation was enough to decrease the surface free energy (SFE) of copolymer film to a very low value of 9.7mJ/m2. In addition, the increase in the Zonyl-TM and BA contents resulted in an increase in the oil repellence of copolymer surfaces which was measured by the contact angles of octane, decane, tetradecane and hexadecane drops.