Abstract Fluorine-containing coatings play an essential role in waterproof paint, but the harm of fluoride to the environment does not meet the current environmental protection requirements. The present study reports an eco-friendly and fluoride-free waterproof hybrid coating prepared by a semi-continuous seed emulsion method employing vinyl tributbutoxy silane (VTBS) as the functional monomer and octyl triethoxysilane modified SiO2 (OTES@ SiO2) as the inorganic filler. In vinyl acetate/butyl acrylate hybrid coatings, the surface covering of OTES@SiO2 and the cross-linking structure produced by VTBS not only significantly improve the thermal stability, mechanical properties, and strong hydrophobicity but also reduce the water absorption. In addition, the gloss loss of the organic–inorganic hybrid layer is <30% after being exposed to UV-irradiation for 720 h. The obtained coating could be a lovely environmental-friendly protective coating for many functional areas, especially for outdoor applications.
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