Enhancing the fraction of grafted polystyrene on silica hybrid nanoparticles

Polymer-grafted inorganic nanoparticles are being developed for a diverse array of applications, ranging from drug delivery to multifunctional composites. In many instances, performance of these core-shell hybrids is limited by relatively broad distributions of size and composition, as well as the presence of impurities, such as unattached polymer chains. Herein, further synthetic improvements, and associated characterization techniques, to enhance the fraction of the grafted polystyrene shell on silica hybrid nanoparticles are discussed. We found that during surface-initiated atom transfer radical polymerization (SI-ATRP) from the silica nanoparticles, thermal self-initiation of styrene produces unattached polymer chains. Size exclusion chromatography afforded a facile approach to quantify the mass of the unattached polymer, and provide a substantial refinement to estimates of chain graft density beyond traditionally-used approaches, such as thermogravimetry. This fraction of unattached polymer is still present even after post-polymerization work-up via precipitation and re-dissolution. Removal necessitates additional procedures, such as high speed centrifugation. Selection of a lower polymerization temperature, in concert with a more reactive Cu complex, significantly reduces the amount of unattached polystyrene impurity. The improved polymerization conditions and post-polymerization purification provide more refined polystyrene-grafted silica nanoparticles to clarify structure-property relationships of these core-shell hybrids.