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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
Author(s) -
Raquez JeanMarie,
Vanderstappen Sophie,
Meyer Franck,
Verge Pierre,
Alexandre Michael,
Thomassin JeanMichel,
Jérôme Christine,
Dubois Philippe
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100496
Subject(s) - crystallinity , caprolactone , materials science , diol , furfuryl alcohol , diels–alder reaction , polymer , methylene , crystallization , polymer chemistry , chemistry , organic chemistry , composite material , polymerization , catalysis
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.