The introduction of dynamic covalent bonds into cross-linked polymer networks enables the development of strong and tough materials that can still be recycled or repurposed in a sustainable manner. To achieve the full potential of these covalent adaptable networks (CANs), it is essential to understand�and control�the underlying chemistry and physics of the dynamic covalent bonds that undergo bond exchange reactions in the network. In particular, understanding the structure of the network architecture that is assembled dynamically in a CAN is crucial, as exchange processes within this network will dictate the dynamicmechanical material properties. In this context, the introduction of phase separation in different network hierarchies has been proposed as a useful handle to control or improve the material properties of CANs. Here we report�for the first time�how Raman confocal microscopy can be used to visualize phase separation in iminebased CANs on the scale of several micrometers. Independently, atomic force microscopy (AFM) confirmed the phase-separated domains inside the polymer. Remarkably, the materials were found to undergo phase separation despite being built up from miscible monomers, which arguably should yield homogeneous materials. We found that the phase separation not only affected the appearance of the material but�more notably�also had a noticeable effect on the thermal-mechanical properties of the material: CANs (of equal aliphatic/aromatic monomer composition) that displayed phase separation had both a higher crossover temperature (T cross , where tan(δ) = 1, and where the material transits from a rubbery to a viscous state) and an increased elastic modulus (G′). By modifying the CAN architecture, we were able to either suppress or enhance the phase separation, and we propose that the phase separation is driven by favorable π−π interactions between the aromatic components. Our work further shows the importance of phase separation in CANs, including in networks built from miscible components, and provides a handle to control the dynamic material properties. Moreover, our work underlines the suitability of Raman imaging as a method to visualize phase separation in CANs.

Phase separation phenomena have been studied widely in the field of polymer science, and were recently also reported for dynamic polymer networks (DPNs). The mechanisms of phase separation in dynamic...