Self-healing and polymer welding of soft and stiff epoxy thermosets via silanolates

Incorporating dynamic bonds into polymers enables static thermosets to be transformed into active materials, possessing the reprocessability of thermoplastics while maintaining the bulk properties of fully crosslinked networks. This new class of materials, termed covalent adaptable networks (CANs), has helped bridge the gap between traditional thermosets and thermoplastics. Here, epoxy-based adaptable networks were synthesized by combining a diepoxide monomer with an oligosiloxane prepolymer containing aminopropyl groups, which crosslink irreversibly, and silanolate end-groups, which participate in dynamic bonding. Two separate diepoxide crosslinkers were used to give a range of soft to stiff materials with a Young's modulus varying from 12 MPa to 2.2 GPa. This study documents how the thermal and mechanical properties (e.g., glass transition temperature and modulus) are affected by compositional changes in these silanolate networks. Dynamic bonding also results in self-healing properties, offering the ability to repair structural polymers and composites. When combined with tunable mechanical properties, self-healing capabilities make these materials well-suited to be sustainable alternatives for many traditional thermosets. For example, we demonstrated the ability to weld a stiff epoxy thermoset to a dissimilar soft material, a feature traditional epoxies do not permit.