Fabrication of thermally resistant and mechanically flexible polyimide foams with anisotropic pore structures for thermal insulation and irradiation tolerance applications

Flexible polyimide foams (PIFs) demonstrate a great potential for applications in the fields of thermal insulation, flame retardancy and irradiation tolerance. In this work, mechanically flexible PIFs with anisotropic pore structure were prepared by adopting the copolymerization strategy and microwave-assisted foaming process. The copolymerization reaction was conducted to synthesize polyester ammonium salt (PEAS) precursors using 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA) as dianhydride, 4,4′-diaminodiphenyl ether (ODA) and 4,4′-diaminodiphenyl sulfone (DDS) as the copolymerized diamines; afterwards, PEAS powders with particle sizes ranging from 100 to 300 μm were obtained by drying, crushing and sieving treatments, which were used as the feedstock for "bottom-up" microwave-assisted foaming and thermal imidization process, thereby leading to the formation of PIFs with regular three-dimensional near-spherical pores in vertical direction (parallel to the pore growth direction) and the aligned ellipsoidal strip-like pore structure in horizontal direction. The directional growth of foam pores resulted in anisotropic mechanical flexibility and thermal insulation performance. Moreover, PIFs possessed excellent thermal stability and flame retardancy with the initial thermal degradation temperature higher than 545 °C and limited oxygen index up to 58.8%. The PIFs exhibited exceptional thermal insulation performance with thermal conductivity values ranging from 0.0276 to 0.0517 W/(m·K) between 25 and 300 °C. Additionally, the PIFs demonstrated excellent irradiation tolerance, with the mechanical and thermal stability retention rate being above 96% after the irradiation experiment (radiation dosage: 1.15 × 105 Gy) using 60Co source. Thus, lightweight PIFs with superior high temperature thermal insulation performance, flame retardancy and irradiation tolerance were successfully prepared, which showed potential applications in aerospace, medical and nuclear power sectors.