Combining Associative and Dissociative Dynamic Linkages in Covalent Adaptable Networks from Biobased 2,5-Furandicarboxaldehyde

Covalent adaptable networks (CAN) emerged as a recent class of polymers that combine the most interesting advantages of thermosets and thermoplastics. In this frame, combining different dynamic linkages within the polymer network could be an interesting approach to finely tune the material properties and determine the extent of their behaviors. Here, we report the synthesis of novel dually crosslinked CAN in which dynamic associative imine linkages and dissociative Diels–Alder adducts were both obtained by exploiting the chemistry of a single biobased building block, 2,5-furandicarboxaldehyde (FDC). Thanks to the favorable chemical environment of the furan ring in a linear polyimine based on FDC, very fast coupling with maleimides in Diels–Alder reactions was reported, leading to the formation of polymer networks in remarkably short times. The obtained sustainable polymer systems were shown to have a behavior in-between those of vitrimers and dissociative CANs, with tunable mechanical behavior and excellent reprocessability.