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.