Abstract
Supramolecular associations provide a promising route to functional materials with properties such as self-healing, easy recyclability or extraordinary mechanical strength and toughness. The latter benefit especially from the transient character of the formed network, which enables dissipation of energy as well as regeneration of the internal structures. However, recent investigations revealed intrinsic limitations in the achievable mechanical enhancement. This manuscript presents studies of a set of telechelic polymers with hydrogen-bonding chain ends exhibiting an extraordinarily high, almost glass-like, rubbery plateau. This is ascribed to the segregation of the associative ends into clusters and formation of an interfacial layer surrounding these clusters. An approach adopted from the field of polymer nanocomposites provides a quantitative description of the data and reveals the strongly altered mechanical properties of the polymer in the interfacial layer. These results demonstrate how employing phase separating dynamic bonds can lead to the creation of high-performance materials.