Photopolymerization-based 4D-printing of shape-memory materials containing high-performance polymers

High-performance aromatic heterochain polymers are engineering thermoplastics with exceptional mechanical and thermal properties that have attracted great interest in various areas ranging from aerospace to biomedicine. However, there have been a number of difficulties to 3D-print materials based on such polymers with new promising performance characteristics. Herein, a number of new photosensitive compositions (PSCs) based on high-performance polyetherimide (PEI) or polysulfone (PSU), reactive functional monomer (N,N-dimethylacrylamide) and oligomer (bisphenol A ethoxylate diacrylate) has been developed. It has been shown that the use of the developed PSCs allows the formation of 3D-structures with high printing resolution by LCD 3D-printing. Subsequent thermal post-curing of 3D-printed green-state samples at 250°С for 1 h led to the fabrication of materials with the highest tensile strength (up to 41.9 ± 3.1 MPa), glass transition temperature (141 °C) and thermal stability (above 350 °C). In addition, 3D-printed structures demonstrate high-temperature shape memory effect with shape fixity ratio > 99% and shape recovery ratio up to 97.1%.