Synthesis and aqueous solution properties of polyelectrolyte-grafted silica particles prepared by surface-initiated atom transfer radical polymerization

A range of polyelectrolyte-grafted silica particles have been prepared by grafting suitable initiators onto near-monodisperse, 304-nm-diameter silica particles using siloxane chemistry, followed by surface-initiated atom transfer radical polymerization (ATRP) of four ionic vinyl monomers, namely sodium 4-styrenesulfonate (SStNa), sodium 4-vinylbenzoate (NaVBA), 2-(dimethylamino)ethyl methacrylate (DAM), and 2-(diethylamino)ethyl methacrylate (DEA) in protic media. The resulting polyelectrolyte-grafted silica particles were characterized using dynamic light scattering (DLS), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), helium pycnometry, and diffuse reflectance infrared Fourier transfer spectroscopy (DRIFTS). The TGA results indicated that the polyelectrolyte contents of the silica particles could be varied from 0.6% to 6.0% in weight. SEM studies revealed several surface morphologies for the grafted polyelectrolytes and XPS analysis of the particle surface also provided good evidence for surface grafting. Combined aqueous electrophoresis and DLS studies confirmed that these polyelectrolyte-grafted silica particles had pH-dependent colloid stabilities, as expected. Cationic polyelectrolyte-grafted silica particles were colloidally stable at low or neutral pH, but became aggregated at high pH. Conversely, anionic polyelectrolyte-coated silica particles became unstable at low pH. It was found that the rate of surface-initiated ATRP was substantially slower than the analogous solution polymerization. Finally, there was some evidence to suggest that, at least in some cases, a significant fraction of polymer chains became detached from the silica particles during polymerization.