With environmental and health issues being raised, researchers have shifted their study from fluorinated to fluorine-free waterproof agents. However, most of the reported fluorine-free water repellents exhibit a significant drawback in their poor stability and durability of water repellency. In addition, the use of higher concentrations in these repellents results in the fabric becoming stiff, which negatively impacts the hand of the treated fabrics. To address these issues, dendrimer-like waterborne polyurethane prepolymers were initially synthesized using isophorone diisocyanate, polytetrahydrofuran, N-methyldiethanolamine, and trimethylolpropane as the primary materials. In this synthesis, sorbitan tristearate served as the dendrimer-like blocking agent, while single-ended bis-hydroxypropyl silicone oil was employed as functional monomers to enhance the hand and water repellency of the prepolymers. Then, dendrimer-like waterborne polyurethane was finished on the cotton fabric using a pad–dry–cure procedure. The test results showed that the water contact angle of dendrimer-like waterborne polyurethane film increased from 104.28° to 107.00° with the content of single-ended bis-hydroxypropyl silicone oil increasing, and the water contact angle of dendrimer-like waterborne polyurethane-finished fabrics reached 148.6° alone with a standard spray test rating of 90–95. In addition, the water contact angle of dendrimer-like waterborne polyurethane-finished fabrics was still greater than 140° even after five standard washes. The single-ended bis-hydroxypropyl silicone oil addition facilitated similar hand to the original fabric in dendrimer-like waterborne polyurethane-finished fabrics with high concentrations, surpassing market water repellents. This work is of great significance for improving the stability and durability of water repellency, and the hand of waterborne polyurethane fluorine-free water repellents in the textile industry.
