Waterproof and Breathable Polyurethane Membranes with Self-Healing and Self-Cleaning Properties: Synergistic Enhancement by Polydimethylsiloxane and Phenolic Carbamate Network and Photocatalytic Effect

Developing environmentally friendly, multifunctional waterproof and breathable membranes (WBMs) has attracted extensive attention and is of great significance but remains challenging. Herein, an environmentally friendly and multifunctional waterborne polyurethane WBM with self-healing and self-cleaning properties is developed in two steps. Firstly, by using polydimethylsiloxane (PDMS) as a hydrophobicity giver and tannic acid (TA) as a crosslinker, a dual-modified waterborne polyurethane (PTWPU) is prepared, which has high surface hydrophobicity due to the surface enrichment of siloxane segments and self-healing performance from the formation of a dynamic phenolic carbamate network. Secondly, by incorporating titanium dioxide (TiO2) photocatalyst nanoparticles to increase internal porosity and establish hydrophilic pathways, a multifunctional waterborne polyurethane WBM (TPTWPU) is developed. This membrane features further enhanced surface hydrophobicity from generated micro-roughness and effective self-cleaning performance, because TA acts as an electron trap to promote the photocatalytic activity of TiO2. The TPTWPU membrane shows good hydrophobicity (water contact angle of 115.3°) and satisfactory moisture permeability of 135.0 g/(m2·24 h), which is 61.2% higher than unmodified membranes. Furthermore, it exhibits efficient self-healing, with a recovery rate exceeding 80% within 2 h. This feasible strategy will provide guidance for materials design in multifunctional coatings for textiles and leather.