A multiscale chemomechanics theory for the solvent – Assisted recycling of covalent adaptable network polymers

Thermosetting polymers are hard to be recycled using conventional methods due to their permanently crosslinked networks. It was recently reported that covalent adaptable network (CAN) polymers could be fully decomposed in organic solvents utilizing bond-exchange reactions (BERs). Re-polymerization occurs by heating the decomposed solution to evaporate the solvent. This prominent feature of CANs provides exciting opportunities to enable the green and sustainable recycling of thermosets. In this paper, we develop a multiscale chemomechanics theory to study the re-polymerization process of CANs, where the soluble chain segments connect at the tails via BERs. At the macromolecular level, the chemical reaction rates are formulated by considering the distance and diffusivity of reactive species, which determine the average chain segment length and network degree of curing (DoC). The evolution rule of DoC is then fed into the continuum-level multi-branched model to capture the thermomechanical properties of CANs at different curing states. The established theory can predict the conversion ratio of functional groups, solution viscosity, volume shrinkage, and glass transition behaviors of re-polymerizing CANs. It also reveals the influencing mechanisms of various material and processing conditions, which paves the road for the immediate engineering applications of the green and sustainable recycling approach for thermosets and their composites.