The demand of water-resistant and breathable materials applied to a separation medium and protective garments is steadily increasing. Typical approaches to obtain these functional materials are based on hydrophobic agents and porous substrates with small fiber diameter, tiny pore, and high porosity. However, a fluorinated hydrophobic finishing agent usually employed in providing effective waterproofness is limited with respect to their environmental persistence and toxic potential. Herein, with the aim to keep a balance between the water-resistance and breathability as well as mechanical properties, we fabricate a novel fluoride-free functional membrane by electrospun polyacrylonitrile (PAN) nanofibers modified with polydimethylsiloxane (PDMS). As determined by morphological, DSC, and FT-IR analyses, the curing reaction of PDMS macromolecules formed an abundance of hydrophobic adhesive structures, which improved the waterproof performance dramatically and imparted relative good breathability at the same time. By systematically tuning the curing temperature as well as the concentration of PDMS, the modified PAN membranes with 4 wt % PDMS possessed good water-resistance (80.9 kPa), modest vapor permeability (12.5 kg m-2 d-1), and air permeability (9.9 mm s-1). Compared with pristine PAN membranes, the modified membranes were endowed with enhanced tensile stress of 15.7 MPa. The good comprehensive performance of the as-prepared membranes suggested their potential applications in protective clothing, membrane distillation, self-cleaning materials, and other medical products. Furthermore, the proposed relationship between porous structure and waterproof/breathable property as one considerable principle is applicable to designing functional membranes with different levels of protective and comfortable performance.
Keywords: electrospinning; poly(dimethylsiloxane); polyacrylonitrile; surface modification; waterproof/breathable.