Facile Preparation of Fluorine‐Free, Heat‐Resisting, Breathable, and Waterproof Nanofibrous Membranes from Polymers of Intrinsic Microporosity

Abstract Waterproof and breathable membranes (WBMs) are widely applied in garment, electronics, and aerospace, however, it is challenging to fabricate WBMs by a facile and successive strategy with excellent comprehensive properties, including environmental friendliness, heat‐resistance, waterproofness, breathability, and mechanical properties. Herein, a straightforward method is developed to fabricate large‐sized WBMs with outstanding integrated performance by direct electrospinning of original polymerization solution from polymers of intrinsic microporosity (PIMs). As‐prepared nanofibrous WBMs perform comprehensive properties with the absence of fluorine, average nanofiber diameters of 278 nm, waterproofness of 88.7 kPa, breathability of 11.2 kg m −2 d −1 , tensile strength of 4.2 MPa, and heat‐resistance of 200 °C, which are superior to most of that reported fluorine‐free WBMs. Most significantly, the avoidance of tedious and intermittent fabrication procedures to prepare high‐performant WBMs allows the achievement of the successive production, and the high heat‐resistance meets the requirement of harsh service conditions. This work not only confirms that PIMs can be a good candidate for preparing high‐performant WBMs, but also paves a new version for fabricating environmental benign WBMs in a facile and successive approach.