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Design of Cross-Linked Semicrystalline Poly(ε-caprolactone)-Based Networks with One-Way and Two-Way Shape-Memory Properties through Diels–Alder Reactions

✍ Scribed by Dr. Jean-Marie Raquez; Sophie Vanderstappen; Dr. Franck Meyer; Dr. Pierre Verge; Dr. Michael Alexandre; Dr. Jean-Michel Thomassin; Prof. Christine Jérôme; Prof. Dr. Philippe Dubois


Publisher
John Wiley and Sons
Year
2011
Tongue
English
Weight
692 KB
Volume
17
Category
Article
ISSN
0947-6539

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✦ Synopsis


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.