Fabrication of Waterborne Silicone-Modified Polyurethane Nanofibers for Nonfluorine Elastic Waterproof and Breathable Membranes

Waterproof and breathable membranes have a huge market demand in areas, such as textiles and medical protection. However, existing fluorinated nanofibrous membranes, while possessing good waterproof and breathable properties, pose health and environmental hazards. Consequently, fabricating fluorine-free, eco-friendly waterborne membranes by integrating outstanding waterproofing, breathability, and robust mechanical performance remains a significant challenge. Herein, we successfully prepared waterborne silicone-modified polyurethane nanofibrous membranes with excellent elasticity, waterproofing, and breathability properties through waterborne electrospinning, using a small quantity of poly(ethylene oxide) as a template polymer and in situ doping of the poly(carbodiimide) crosslinking agent, followed by a simple hot-pressing treatment. The silicone imparted the nanofibrous membrane with high hydrophobicity, and the crosslinking agent enabled its stable porous structure. The hot-pressing treatment (120 °C) further reduced the pore size and improved the water resistance. This environmentally friendly nanofibrous membrane showed a high elongation at break of 428%, an ultra-high elasticity of 67.5% (160 cycles under 400% tensile strain), an air transmission of 13.2 mm s−1, a water vapor transmission rate of 5476 g m−2 d−1, a hydrostatic pressure of 51.5 kPa, and a static water contact angle of 137.9°. The successful fabrication of these environmentally friendly, highly elastic membranes provides an important reference for applications in healthcare, protective textiles, and water purification.