Shape Memory Behavior of Emulsion-Templated Poly(ϵ-Caprolactone) Synthesized by Organocatalyzed Ring-Opening Polymerization

Organocatalyzed ring-opening polymerization (ROP) of ϵ-caprolactone (CL) and 4,4′-bioxepanyl-7,7′-dione as a bis-lactone cross-linker was performed within the oil-in-oil high internal phase emulsions (HIPEs) at 50 °C. In this way, the cross-linked poly(ϵ-caprolactone) (PCL) polyHIPE foams of ∼85% porosity were synthesized. Thermomechanical properties of the prepared polyHIPEs were studied and proved to greatly depend on a degree of PCL cross-linking. The melting and crystallization temperatures as well as the degree of crystallinity of PCL polyHIPE foams decrease with an increasing cross-linking degree. Semi-crystalline polyHIPEs demonstrate shape memory behavior with excellent shape fixity and shape recovery. At an appropriate degree of PCL cross-linking, the polyHIPE temporary shape can be fixed at room temperature, while a transition to the permanent shape occurs upon heating at 40 °C. Moreover, a two-way shape memory behavior of the PCL polyHIPEs under constant stress was observed.