Study of a Novel Fluorine-Containing Polyether Waterborne Polyurethane with POSS as a Cross-Linking Agent

Waterborne polyurethane are more eco-friendly materials due to lower volatile organic compounds (VOCs, mainly isocyanates) content than the alternative materials. However, these rich hydrophilic groups polymers have not yet reached good mechanical properties, durability and hydrophobicity behaviors. Therefore, hydrophobic waterborne polyurethane has become a research hotspot, attracting significant attention. In this work, firstly, a novel fluorine-containing polyether P(FPO/THF) was synthesized by cationic ring-opening polymerization of 2-(2,2,3,3-tetrafluoro-propoxymethyl)-oxirane (FPO) and tetrahydrofuran (THF). Secondly, fluorinated polymer P(FPO/THF), isophorone diisocyanate (IPDI) and hydroxy-terminated polyhedral oligomeric silsesquioxane (POSS-(OH)₈) were used to prepare a new fluorinated waterborne polyurethane (FWPU). Hydroxy-terminated POSS-(OH)₈ was used as a cross-linking agent, while dimethylolpropionic acid (DMPA) and triethylamine (TEA) were used as a catalyst. Four kinds of waterborne polyurethanes (FWPU0, FWPU1, FWPU3, FWPU5) were obtained by adding different contents of POSS-(OH)₈ (0%, 1%, 3%, 5%). The structures of the monomers and polymers were verified by ¹H NMR and FT-IR, and the thermal stabilities of various waterborne polyurethanes were analyzed by thermogravimetric analyzer (TGA) and differential scanning calorimetry (DSC). As the results, the thermal analysis showed that the FWPU performed the good thermal stability and the glass transition temperature could reach at about -50 °C. The FWPU1 film exhibited that the elongation at break was 594.4 ± 3.6% and the tensile strength at break was 13.4 ± 0.7 MPa, elucidating that the FWPU1 film developed the excellent mechanical properties relative to the alternative FWPUs. Further, the FWPU5 film performed the promising properties, including the higher surface roughness of FWPU5 film (8.41 nm) obtained by the atomic force microscope (AFM) analysis, and the higher value of water contact angle (WCA) at 104.3 ± 2.7°. Those results illustrated that the novel POSS-based waterborne polyurethane FWPU containing a fluorine element could develop the excellent hydrophobicity and mechanical properties.