Frontally polymerizable shape memory polymer for 3D printing of free-standing structures

Four-dimensional (4D) printing is used to describe three-dimensional (3D)-printed objects with properties that change over time. Shape memory polymers (SMPs) are representative materials for 4D printing technologies. The ability to print geometrically complex, free-standing forms with SMPs is crucial for successful 4D printing. In this study, an SMP capable of frontal polymerization featuring exothermic self-propagation was synthesized by adding cyclooctene to a poly(dicyclopentadiene) network, resulting in switching segments. The rheological properties of this SMP were controlled by adjusting incubation time. A nozzle system was designed such that the SMP could be printed with simultaneous polymerization to yield a free-standing structure. The printing speed was set to 3 cm min-1 according to the frontal polymerization speed. A free-standing, hexagonal spiral was successfully printed and printed spiral structure showed excellent shape memory performance with a fixity ratio of about 98% and a recovery ratio of 100%, thereby demonstrating the 3D printability and shape memory performance of frontally polymerizable SMPs.