Multifunctional Poly(<i>ϵ</i>‐caprolactone)‐Forming Networks by Diels–Alder Cycloaddition: Effect of the Adduct on the Shape‐Memory Properties

Abstract

Abstract Star‐shaped poly( ϵ ‐caprolactone)s are functionalized by various dienes (furan and anthracene) and a dienophile (maleimide), and the kinetics of network formation by melt‐blending is compared for both Diels–Alder adducts. When curing at 60 °C, the anthracene–maleimide network forms more rapidly and gives rise to a more crosslinked material than with the furan–maleimide adduct. Shape‐memory properties of the networks are compared in terms of Diels–Alder adduct stability. Both materials exhibit excellent fixity and recovery ratios, but the relatively low retro Diels–Alder temperature of the furan–maleimide adduct perturbs the mechanical stability of the network during cyclic tensile testing between 0 and 60 °C, whereas the anthracene–maleimide adduct is shown to be stable up to 150 °C.