Creation of a PDMS Polymer Brush on SiO₂-Based Nanoparticles by Surface-Initiated Ring-Opening Polymerization

The incorporation of nanoparticles into soft matrices opens a broad spectrum of novel property combinations. However, one of the major challenges for these systems remains the compatibilization of particles with the surrounding matrix by proper surface functionalization. For silicon-based systems or liquid crystalline phases, polydimethylsiloxane (PDMS) brushes at the surface of particles increase the stability against particle agglomeration in such systems. Here, we report a novel approach for the functionalization of particles with a polysiloxane brush by surface-initiated ring-opening polymerization of a cyclosiloxane. For this purpose, surface hydroxy groups of silica and silica-coated hematite particles are used as initiators in combination with phosphazene bases as catalysts. The ring-chain equilibrium of a model-based solution polymerization is investigated in detail to find the appropriate reaction parameters. The corresponding molar masses are determined and compared by ¹H-NMR and SEC measurements to confirm the underlying mechanism. In the resulting hybrid nanostructures, a covalently bound PDMS fraction is achieved up to 47 mass %.