title: Design of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels-Alder reactions.
abstract: Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels-Alder reactions by reactive extrusion. The Diels-Alder and retro-Diels-Alder reactions proved to be useful for enhancing the molecular motion of PCL-based systems, and therefore their crystallization ability, in the design of cross-linked semicrystalline polymers with one-way and two-way shape-memory properties. Successive reactions between α,ω-diol PCL (PCL(2) ), furfuryl alcohol, and methylene diphenyl 4,4'-diisocyanate straightforwardly afforded the α,ω-furfuryl PCL-based PUR systems, and subsequent Diels-Alder reactions with N,N-phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross-linking density could be modulated by partially replacing PCL-diol with PCL-tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross-linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape-memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one-way and two-way shape-memory properties depending on their cross-linking density.
authors: Laboratory of Polymeric and Composite Materials, Center of Innovation and Research in Materials and Polymers, University of Mons, Place du Parc 20, 7000 Mons, Belgium. jean-marie.raquez@umons.ac.be
authors: Jean-Marie
authors: JM
authors: Raquez
authors: Sophie
authors: S
authors: Vanderstappen
authors: Franck
authors: F
authors: Meyer
authors: Pierre
authors: P
authors: Verge
authors: Michael
authors: M
authors: Alexandre
authors: Jean-Michel
authors: JM
authors: Thomassin
authors: Christine
authors: C
authors: Jérôme
authors: Philippe
authors: P
authors: Dubois
mesh_terms: D003460:Crystallization; D004548:Elasticity; D011091:Polyesters / Q000138:chemical synthesis* / Q000737:chemistry*; D011140:Polyurethanes / Q000138:chemical synthesis*
chemical_list: D011091:Polyesters; D011140:Polyurethanes; C081821:microthane foam; C016240:polycaprolactone