Emulsion copolymerization of fluorinated acrylate in the presence of a polymerizable emulsifier

An emulsifier-free fluorinated polyarcylate emulsion was synthesized by a seed emulsion polymerization method from methyl methacrylate (MMA), butyl acrylate (BA) and hexafluorobutyl methacrylate (HFMA) in the presence of a polymerizable emulsifier—ammonium allyloxtmethylate nonylphenol ethoxylates sulfate (DNS-86). Influences of the DNS-86 level on electrolyte stability of the emulsifier-free emulsion were discussed. In addition, the emulsion and the films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H NMR) spectrometry, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), thermogravimetry (TG), and contact angle (CA) analysis, respectively. The FT-IR spectra and ¹H NMR spectrum showed that HFMA was effectively involved in the emulsion copolymerization and monomers formed the fluorine-containing acrylate copolymer. The resulted emulsion particles had a core–shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed along the depth profile of the fluorine-containing emulsion film. One side of the film was richer in fluorine and more hydrophobic than the other side. The film formed from the fluorine-containing emulsion showed higher thermal stability than that of the fluorine-free emulsion.