Extended Chemical CrossLinking of a Thermoplastic Polyimide: Macroscopic and Microscopic Property Development

Polyimides are well established as gas separation membranes due to their intrinsically low free volume and correspondingly high H2 selectivity relative to other gases such as CO2. Prior studies have established that H2/CO2 selectivity can be improved by crosslinking polyimides with diamines differing in spacer length. In this work, we follow the evolution of macroscopic and microscopic properties of a commercial polyimide over long crosslinking times (tx) with 1,3‐diaminopropane. According to spectroscopic analysis, the crosslinking reaction saturates after ≈24 h, whereas tensile, nanoindentation and stress relaxation tests reveal that the material stiffens, and possesses a long relaxation time that increases with increasing tx. Although differential scanning calorimetry shows that the glass transition temperature decreases systematically with increasing tx, permeation studies indicate that the permeabilities of H2 and CO2 decrease, while the H2/CO2 selectivity increases markedly, with increasing tx. At long tx, the polyimide becomes impermeable to CO2, suggesting that it could be used as a barrier material. magnified image