Thermal Guanidine Metathesis for Covalent Adaptable Networks.

We demonstrate that a dynamic chemical reaction that we term thermal guanidine metathesis (TGM) can serve as the basis for covalent adaptable network (CAN) materials. CANs are a class of cross-linked polymers that transition from thermoset to thermoplastic-like rheological behavior upon significant activation of reversible exchange reactions within the network and thus can be reprocessed. Small molecule studies indicate the TGM reaction proceeds by a dissociative mechanism, and guanidine-cross-linked network polymers can be reprocessed at elevated temperature. These TGM-based CANs exhibit dynamic behavior, such as dissolution in the presence of monofunctional exchange partners and stress relaxation above . Additionally, differences in the activation energies obtained by small molecule kinetic studies and stress relaxation analysis are consistent with key predictions of the Semenov-Rubinstein model of thermoreversible gelation of highly cross-linked networks.