Controlling Surface Segregation of a Polymer To Display Carboxy Groups on an Outermost Surface Using Perfluoroacyl Groups

Controlling the surface properties of solid polymers is important for practical applications. We here succeeded in controlling the surface segregation of polymers to display carboxy groups on an outermost surface, which allowed the covalent immobilization of functional molecules via the carboxy groups on a substrate surface. Random methacrylate-based copolymers containing carboxy groups, which were protected with perfluoroacyl (R_f) groups, were dip-coated on acrylic substrate surfaces. X-ray photoelectron spectroscopy and contact-angle measurements revealed that the R_f groups were segregated to the outermost surface of the dip-coated substrates. The R_f groups were removed by hydrolysis of the R_f esters in the copolymers, resulting in the display of carboxy groups on the surface. The quantification of carboxy groups on a surface revealed that the carboxy groups were reactive to a water-soluble solute in an aqueous solution. The surface segregation was affected by the molecular structure of the copolymer used for dip-coating