High-Temperature Shape Memory Behavior of Semicrystalline Polyamide Thermosets

We have explored semicrystalline poly­(decamethylene terephthalamide) (PA 10T) based thermosets as single-component high-temperature (>200 °C) shape memory polymers (SMPs). The PA 10T thermosets were prepared from reactive thermoplastic precursors. Reactive phenylethynyl (PE) functionalities were either attached at the chain termini or placed as side groups along the polymer main chain. The shape fixation and recovery performance of the thermoset films were investigated using a rheometer in torsion mode. By controlling the <i>M</i>_n of the reactive oligomers, or the PE concentration of the PE side-group functionalized copolyamides, we were able to design dual-shape memory PA 10T thermosets with a broad recovery temperature range of 227–285 °C. The thermosets based on the 1000 g mol^–1 reactive PE precursor and the copolyamide with 15 mol % PE side groups show the highest fixation rate (99%) and recovery rate (≥90%). High temperature triple-shape memory behavior can be achieved as well when we use the melt transition (<i>T</i>_m ≥ 200 °C) and the glass transition (<i>T</i>_g = ∼125 °C) as the two switches. The recovery rate of the two recovery steps are highly dependent on the crystallinity of the thermosets and vary within a wide range of 74%–139% and 40–82% for the two steps, respectively. Reversible shape memory events could also be demonstrated when we perform a forward and backward deformation in a triple shape memory cycle. We also studied the angular recovery velocity as a function of temperature, which provides a thermokinematic picture of the shape recovery process and helps to program for desired shape memory behavior