Green strategy based on supercritical-fluid foaming for fabricating rigid microcellular thermoplastic polyimide foams with ultrahigh compressive strength

Thermosetting polyimide (PI) foams (PIFs) are usually synthesized through chemical foaming; however, this approach is environmentally toxic, and it is difficult to regulate the cell structure, remold the foam, and increase the foam compressive strength. The development of microcellular PIFs with ultrahigh compressive strength and high volume expansion ratio remains a challenge. Herein, thermoplastic PI with a branched structure and flexible ether bonds was synthesized through solution polymerization, and microcellular thermoplastic PIFs (TPIFs) with ultrahigh strength were fabricated via supercritical-carbon-dioxide foaming using 2,4,6-triamino pyrimidine (TAP) as a chain-extender monomer. Subsequently, a lattice model of a closed tetrakaidecahedral cell was used to clarify the relation between the foam compressive strength and polymer cell structure. Experimental results indicate that the optimal thermal imidization temperature is 230 °C and that the resulting branched structure considerably improves viscoelasticity, flame retardancy, and foaming performance. A TAP content of 0.75 g results in branched-structure TPIFs with a mean cell size of 16.8 μm. Notably, at high temperatures and pressures, the compressive strength of TPIFs with 0.75 g TAP is more than nine times of that of TPIFs without TAP. Increasing the TAP content beyond 0.75 g results in a crosslinked structure. Backward differentiation shows that TPIF compression is constant at 0.14–0.18 in the [0,0,1] lattice direction. The proposed physical foaming method is environment-friendly and can sustainably produce TPIFs with a high volume expansion ratio, an adjustable microcellular structure, and outstanding mechanical properties.