Thiol‐ene Reaction as Reversible Covalent Bond for the Design of Shape‐Memory Polymers

Abstract Besides a stable phase, shape‐memory polymers require an additional switchable moiety. In addition to thermal transitions and supramolecular interactions, these units can also be based on covalent bonds. Herein, the use of the reversible thiol‐ene reaction as reversible cross‐linker for the design of shape‐memory polymers is demonstrated. A facile route to polymer networks with a thiol‐ene acceptor and a comonomer (butyl methacrylate or 2‐ethylhexyl methacrylate) cross‐linked by dithiols is introduced. The thermal and mechanical properties of the resulting polymers are characterized in detail. Hereby, the polymers feature excellent shape‐memory behavior with fixity and recovery rates above 90%. This study shows that the thiol‐ene cross‐linker can function as both, the stable and the switchable structural moiety rendering the usage of a covalent cross‐linker unnecessary. This partial reversibility can also be proven by temperature‐depending Raman spectroscopy.