Objective Water-based acrylic resins have been widely adopted in various industrial sectors, including coatings, adhesives and leather finishing, owing to their environmental friendliness, non-toxicity, excellent film-forming properties and low production costs. However, their poor water and stain resistance, coupled with insufficient chemical stability, severely limit their expansion into high-end functional applications. Organic fluorine modification is an effective technical approach for enhancing the performance of acrylic resins; however, traditional long-chain perfluoroalkyl compounds pose bioaccumulation risks and potential environmental hazards, and are subject to strict restrictions and controls under the Registration, Evaluation, Authorisation and Restriction of Chemicals Regulation.

Methods In this study, the C6 fluorinated monomer, 2-(perfluorohexyl) ethyl methacrylate (FHEMA), was adopted as the modifying monomer, and an emulsion polymerization method was employed to develop an organic fluorine modified water-based acrylic resin system. Six fluorine-free acrylic monomers, including butyl methacrylate (BMA), ethyl methacrylate (EMA), cyclohexyl methacrylate (CHMA), methyl methacrylate (MMA), isobutyl methacrylate (i-BMA) and vinyl neodecanoate (VND), were copolymerized, respectively, with ethyl acrylate (EA). The monomers were screened by measuring the surface energies of the copolymer films via the OWRK method. The results showed that the surface energies of the copolymer films formed by BMA, EMA and CHMA with EA did not differ significantly from that of the EA homopolymer film ( 65.9 mJ/m² ); whereas the surface energies of the copolymer films of MMA, i-BMA, and VND with EA decreased to 30.6 mJ/m², 28.2 mJ/m² and 23.0 mJ/m², respectively, demonstrating their superior hydrophobic and oleophobic properties. Based on these results, MMA, i-BMA and VND were copolymerized, respectively, with FHEMA to prepare the PS_X series of organic fluorine modified water-based acrylic resins.

Results Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed that FHEMA had been successfully incorporated into the acrylic resin molecular chains. Thermogravimetric analysis and differential scanning calorimetry indicated that the PS₄ resin film exhibited a thermal decomposition temperature of 349.3 ℃ and a glass transition temperature of 73.01 ℃ demonstrating significantly improved thermal stability compared with the unmodified resin. Its water contact angle and the diiodomethane contact angle reached 121.7° and 93.3°, respectively, and the surface energy was reduced to 11.3 mJ/m², resulting in substantially enhanced hydrophobic and oleophobic properties. Furthermore, the PS₄ resin film maintained a light transmittance of 98.20%-99.20%, a Shore hardness of 99.43 HA, and a water absorption rate of only approximately 3%, confirming its excellent optical transparency, mechanical hardness and water resistance. This resin coating effectively resisted the adhesion of common contaminants such as coffee, lipstick and oil-based markers, and these contaminants can be completely removed by simple wiping, demonstrating the coating’s excellent anti-soiling properties.

Conclusions Through systematic screening of fluorine-free acrylate monomers and optimization of the formulation, the surface energy of the organic fluorine modified acrylate resin film can be effectively reduced, significantly enhancing its hydrophobic, oleophobic and anti-soiling properties. This study provides a feasible technical solution and theoretical basis for the industrial production of high-performance water-based stain-resistant acrylic resins, and is of great significance for promoting the expansion of water-based acrylic resins into high-end applications.