A kaolinite-polymer intercalation complex was apparently formed for the first time by the polymerization of acrylonitrile between the kaolinite layers. A kaolinite-ammonium acetate intercalation complex was dispersed in acrylonitrile monomer. The monomer was apparently incorporated between the layers by displacing intercalated ammonium acetate. After the removal of excess monomer, the intercalation complex was heated to cause polymerization. The resulting kaolinite-polyacrylonitrile (PAN) intercalate showed a basal spacing of ∼ 13–14 Å. On heating the complex at 220°C for 1 hr in air, the spacing decreased slightly. The hydrogen bond between the hydroxyls of kaolinite and probably the C≡N group of PAN was not affected after heating at 220°C. Even after heating at 400°C, the layers expanded. Because the starting kaolinite-ammonium acetate intercalation complex decomposed at a much lower temperature, these observations strongly suggest the presence of PAN between the layers.

Electrospun membranes have potential applications in the field of waterproof and breathable textile products. However, challenges still exist to improve the breathability, and waterproof and mechanical properties of these microporous membranes. In this paper, a novel hydrophobic microporous nanofiber membrane was prepared via side-by-side electrospinning of fluorosilane-modified silica nanoparticles (F–SiO2) blended with synthesized polyurethane (PU) solution and composited with the polyacrylonitrile (PAN) solution. To prepare F–SiO2, SiO2 nanoparticles were hydrophobically modified by fluorosilane. Composite nanofiber membranes with different blending ratios of PU(F–SiO2)/PAN were fabricated via side-by-side electrospinning by controlling the extruding speed of two spinnerets. Experimental results indicated that regarding F–SiO2 as hydrophobic inorganic particle can improve the hydrophobic properties of PU nanofiber membrane. The prepared PAN/(F–SiO2/PU) nanofiber microporous membranes exhibit relatively excellent waterproof and mechanical properties as that robust tensile strength (19.5 MPa), preferable water vapor permeability [10.3 kg/(m2 d)], favorable water contact angle (137.2°), and superior mechanical properties. It was believed that the reinforced PAN/(F–SiO2/PU) nanofibrous composite membranes have potential applications in chemical protective clothing, army combat uniforms, self-cleaning materials, and other medical products.