Incorporating Functionalized Cellulose to Increase the Toughness of Covalent Adaptable Networks

Covalent adaptable networks (CANs) are cross-linked polymers that have mechanical properties similar to thermosets at operating conditions yet can be reprocessed by cross-link exchange reactions that are activated by a stimulus. Although CAN exchange dynamics have been studied for many polymer compositions, the tensile properties of these demonstration systems are often inferior compared to those of commercial thermosets. In this study, we explore toughening CANs capable of forming covalent bonds with a reactive filler to characterize the trade-off between improved toughness and longer reprocessing times. Polycarbonate (PC) and polyurethane (PU) CANs were toughened by incorporating cellulose modified with cyclic carbonate groups as a reactive filler with loadings from 1.3 to 6.6 wt %. The addition of 6.6 wt % of the cellulose derivative resulted in a 3.2-fold increase in average toughness for the PC CANs, yet it only increased the characteristic relaxation time of stress relaxation (τ*) via disulfide exchange at 180 °C from 63 to 365 s. The cellulose-containing samples also showed >80% recovery in crosslinking density and mechanical properties after reprocessing. The addition of 3.2 wt % of the functionalized cellulose into a polyethylene glycol-based PU CAN led to a 2.3-fold increase in toughness while increasing τ* at 140 °C from 106 to 157 s. These findings demonstrate the promise of functionalized cellulose as an inexpensive, renewable, and sustainable filler that toughens CANs containing hydroxyl groups.