Polyhedral Oligomeric Silsesquioxane‐Capped Poly( n ‐Butyl Acrylate) Copolymers With Supramolecular Quadruple Hydrogen Bonds

In this contribution, we reported the synthesis of polyhedral oligomeric silsesquioxane (POSS)‐capped poly( n ‐butyl acrylate [BA]) copolymer telechelics featuring supramolecular quadruple hydrogen bonds through reversible addition‐fragmentation chain transfer (RAFT) copolymerization of BA with 2‐ureido‐4(1H)‐pyrimidinone acrylate (UPyA). In this work, we investigated the impact of both POSS termini and supramolecular hydrogen bonding interactions on the macromolecular dynamics by means of rheological analysis. Notably, the organic–inorganic hybrids displayed self‐assembly behavior; the terminal POSS cages were aggregated into spherical microdomains with a size of 10–30 nm in diameter. The combination of POSS termini with supramolecular quadruple hydrogen bonds led to physical crosslinking, which bestowed robust mechanical strength on the organic–inorganic telechelics. Furthermore, the crosslinking imparted shape memory behavior to the organic–inorganic telechelics, whereas the dynamic exchange of supramolecular quadruple hydrogen bonds endowed the hybrids with excellent self‐healing properties.