Water repellent is an important functional finish for cotton fabric. However, cotton fabrics often have poor washing resistance and other performances after actual finishing. In this study, based on the structural characteristics of cotton fiber and durability of water repellent, a cross-linked amino long-chain alkyl polysiloxane (CAHPS) was first prepared, and then reacted with modified silica. Finally, a chemically bonded organic–inorganic nanohybrid cross-linked polysiloxane (rSiO2-CAHPS) was fabricated. Furthermore, the rSiO2-CAHPS was emulsified to obtain a durable fluorine-free water repellent. The water repellent finishing for cotton fabric was carried out by the pad–dry–cure process. After finishing, the cotton fabric had good resistance to conventional liquids and excellent washing resistance, and still maintained good water repellency after 30 rounds of soaping. Moreover, properties including air permeability, mechanical property and whiteness are hardly affected after finishing. SEM and XPS characterization show that a layer of dense silicon film is formed on the surface of cotton fabric by rSiO2-CAHPS water repellent. The existence of nanosilica can improve the surface roughness of cotton fibers. The synergistic effect of fiber matrix, nanoparticles and CAHPS endows the fabric with a micro/nano-multi-scale micro-rough structure, which improves the water repellency of cotton fabric after water repellent finishing.

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