Interfacial crosslinking of self‐assembled triblock copolymer nanoparticles via alkoxysilane hydrolysis and condensation

The use of amphiphilic triblock copolymers bearing a reactive alkoxysilane middle block as polymeric stabilizers is reported in this work. A series of poly(ethylene glycol) methyl ether methacrylate‐<i>b</i>‐(3‐trimethoxysilyl)propyl methacrylate‐<i>b</i>‐benzyl methacrylate (PEGMA‐<i>b</i>‐MPS‐<i>b</i>‐BzMA) triblock copolymers were prepared by RAFT solution polymerization and polymerization‐induced self‐assembly (PISA), respectively, where the various block lengths and overall composition were varied. The copolymers prepared by solution polymerization were employed as oil‐in‐water stabilizers where upon application of a catalyst, the 3‐(trimethoxysilyl)propyl methacrylate (MPS) block at the droplet interface was crosslinked to yield capsule‐like structures. The effectiveness of interfacial crosslinking was validated by dynamic light scattering and electron microscopy. <i>In situ</i> self‐assembly by the PISA method resulted in spherical nanoparticles of controllable size that were readily crosslinked by addition of base, with significant enhancement of colloidal stability.