Flame-Retardant and Hydrophobic Cotton via Alkoxysilyl-Functionalized Polysiloxanes, Cyclosiloxanes, and POSS with Surface Thiol-Ene Dithiophosphate Grafting

In this work, a multifunctional surface engineering strategy was developed to impart both flame-retardant and hydrophobic properties to cotton fabrics. In the first stage, cellulose fibers were modified with poly(methylvinyl)siloxane containing trimethoxysilyl groups, 2,4,6,8-tetramethyl-divinyl-bis(trimethoxysilylpropyltioethyl)cyclotetrasiloxane, or tetrakis(vinyldimethylsiloxy)tetrakis(trimethoxysilylpropyltioethyl)octasilsesquioxane (POSS). All modifiers contained alkoxysilyl groups capable of forming covalent bonds with cellulose hydroxyl groups. The modification was performed using a dip-coating process followed by thermal curing. This procedure enabled the formation of Si-O-C linkages and the generation of a reactive organosilicon layer on the cotton surface. In the second step, O,O'-diethyl dithiophosphate was grafted directly onto the vinyl-functionalized fabrics via a thiol-ene click reaction. This process resulted in the formation of a phosphorus- and sulfur-containing protective layer anchored within the siloxane-based network. The obtained hybrid coatings were characterized using Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and SEM-EDS. These analyses confirmed the presence and uniform distribution of the modifiers on the fiber surface. Microscale combustion calorimetry demonstrated a substantial reduction in the heat release rate. Thermogravimetric analysis (TG/DTG) revealed increased char formation and altered thermal degradation pathways. The limiting oxygen index (LOI) increased for all modified fabrics, confirming enhanced flame resistance. Water contact angle measurements showed values above 130°, indicating effective hydrophobicity. As a result, multifunctional textile surfaces were obtained. In addition, the modified fabrics exhibited partial durability toward laundering and retained measurable flame-retardant and hydrophobic performance after repeated washing cycles.