Functional silsesquioxane polymers with branched perfluoroalkyl substituents: Synthesis and prospect applications

• Condensation of alkoxysilanes in an active medium is a powerful and versatile method for the preparation of polysiloxanes of various architectures. • The discussed approach makes it possible to carry out cocondensation in an active medium of alkoxysilanes of different nature and obtain copolymers of different structures. • Silsesquioxane copolymers containing perfluoroalkyl substituents and –SH, –NH2, or –COOH functional groups were used to treat polyamide and cotton fabrics. Condensation of alkoxysilanes in the active medium, which means acetic or trifluoroacetic acids, is a convenient and versatile method for preparing silsesquioxane copolymers with various functional groups. The method does not require the selection of special conditions, the use of additional solvents and catalysts. The obtained copolymers from poorly compatible monomers are homogeneous in composition without the use of additional solvents. Starting from commercially available functional triethoxisilanes and triethoxysilyl derivatives with branched tert -perfluorohexyl substituents (R F = CF 3 CF 2 CF 2 C(CF 3 ) 2 (CH 2 ) 3 -) under condensation in an active medium new functional silsesquioxane polymers with various groups (–NH 2 , –SH, or –COOH) were obtained. The synthesis techniques used provided a high yield of the resulting copolymers (91–94%). Despite the low compatibility of perfluoroalkyl organosilicon compounds with functional alkoxysilanes, the resulting copolymers are homogeneous in composition, which was confirmed by NMR and GPC. Copolymers are effective modifiers for the surface of materials. In particular, they were used as water repellents for cotton and polyamide fabrics. Modified surfaces of cotton and polyamide fabrics acquired highly hydrophobic properties (α ˃ 120°). The presence of –NH 2 , –SH or –COOH groups in the chemical structure of fluorinated silsesquioxane copolymers provided high washing-resistant of modified cotton textile. For polyamide fabric, a similar effect was achieved where copolymers with –NH 2 or –SH groups were used. The COOH-containing copolymer coating on the polyamide textile do not provide resistance of the modified polyamide textile to repeated washing. Thus, we demonstrated that the new functional silsesquioxane polymers with branched perfluoroalkyl substituents and –NH 2 or –SH groups are versatile and efficient hydrophobic agents for both cotton and polyamide textiles.