Synthesis and characterization of novel fluoroalkyl-terminated hyperbranched polyurethane latex

Waterborne polyurethane (PU) emulsions are widely used in various fields and the demand for them is ever-increasing over the years. However, the hydrophilic chain extender inevitably bonded into the PU backbone can affect the water tolerance of PU. Thus, it is of great importance to improve PU water resistance effectively. Herein, novel fluoroalkyl-terminated hyperbranched polyurethane (HBPUF) latex was accordingly synthesized by graft reaction of perfluorohexyl ethyl alcohol and hyperbranched polyurethane (HBPU), which was previously obtained from interaction between hydroxyl-terminated hyperbranched polymer and PU prepolymer manufactured via the acetone process, as well as using neutralization, adding water, and high-speed stirring operations. We characterized the resultants and investigated its surface properties by IR, NMR, TEM, XRD, TGA, DSC, FE-SEM, AFM, XPS, and contact angle measurements, etc. IR and NMR tests confirmed that the fluorinated fragments had been grafted onto the tail end of HBPU. TEM, XRD, DSC, and FE-SEM results all accounted for the fact that there were multi-crystals in PU, HBPU and HBPUF. TGA results showed that thermal stabilities of the PU, HBPU, and HBPUF latex films were enhanced in turn. XPS and AFM analyses demonstrated that the fluorine-containing segments from the HBPUF terminals were prone to migrate and enrich on the film-air surface of the HBPUF latex film, which made water contact angle and water absorption of the HBPUF film be as 113.9° and 11.1%, respectively, compared to those of the PU film (77.8° and 136.2%). This research indicates that water resistance of the PU film can be efficiently enhanced by fluorinated polyurethane with novel fluoroalkyl-terminated hyperbranched structure.