Unravelling the Mechanism of Viscoelasticity in Polymers with Phase-Separated Dynamic Bonds

Incorporation of dynamic (reversible) bonds within polymer structure enables properties such as self-healing, shape transformation, and recyclability. These dynamic bonds, sometimes refer as stickers, can form clusters by phase-segregation from the polymer matrix. These systems can exhibit interesting viscoelastic properties with an unusually high and extremely long rubbery plateau. Understanding how viscoelastic properties of these materials are controlled by the hierarchical structure is crucial for engineering of recyclable materials for various future applications. Here we studied such systems made from short telechelic polydimethyl-siloxane chains by employing a broad range of experimental techniques. We demonstrate that formation of a percolated network of interfacial layers surrounding clusters enhances mechanical modulus in these phase-separated systems, whereas single chain hopping between the clusters results in macroscopic flow. On the basis of the results, we formulated a general scenario describing viscoelastic properties of phase-separated dynamic polymers, which will foster development of recyclable materials with tunable rheological properties.