Overcoming the Tradeoff Between Processability and Mechanical Performance of Elastomeric Vitrimers

Vitrimers are polymer networks with dynamic covalent bonds that allow the network to reconfigure its connectivity while maintaining a constant number of chemical bonds at all temperatures. The melt viscosity of vitrimers thus gradually decreases with temperature. This behavior makes vitrimers more difficult to process than typical thermoplastics using conventional processing techniques, such as extrusion. Although many strategies have been reported to address this issue, it remains challenging to overcome a key tradeoff between improving the processability or the mechanical performance. Herein, this work presents a new strategy for overcoming this tradeoff in the context of elastomeric vitrimers. The approach entails the cross‐linking of a functionalized low‐glass transition (T_g) polymer matrix with an incompatible high‐T_g polymer featuring pendant groups with complementary reactivity. When compared to a conventional homogeneous vitrimer, the microphase‐separated materials prepared by reactive extrusion present improved tensile properties and creep resistance at room temperature while also exhibiting enhanced processability at high temperature. These enhanced properties are a consequence of the combination of the phase separation between the soft and hard phases, the restriction of dynamic cross‐linking reactions within the interfacial zones, and the judicious selection of the T_g of the hard phase to be in between the use and processing temperatures.