Extrudable Covalently Cross‐Linked Thio‐Urethane Liquid Crystalline Elastomers

Abstract Liquid crystalline elastomer networks cross‐linked by dynamic covalent bonds (xLCEs) possess the remarkable capability of being (re)processed during plastic flow at high temperatures, while also allowing for the (re)programming of their local alignment. However, the current generation of xLCEs cannot be extruded directly into filaments or injection‐molded into shapes capable of actuation. Here, a novel poly(thio‐urethane) (PTU) LCE thermoset is presented. The inclusion of dibutyltin dilaurate as a catalyst enables the manipulation of the elastic–plastic transition through two distinct pathways. The dissociative equilibrium exchange between the thio‐urethane linkage to form separate thiol and isocyanate competes with the associative exchange of thio‐urethane and a free isocyanate or thiol groups. The temperature of fast plastic flow onset is ≈160 ˚C, and the associated bond‐exchange activation energy is ≈54 kJ mol⁻¹. The hydrogen bonding below the elastic‐plastic transition makes the elastomer robust and extremely ductile with a failure strain exceeding 600% and a Shore hardness A of 72, preventing any creep during cyclic thermal actuation. The versatility of this dynamically cross‐linked elastomer is successfully demonstrated by extruding it using a commercial twin‐screw extruder, injection molding it into required shapes, and hot‐pressing it into flat films or shapes.