Preparation of Silica/Polymer Hybrid Nanoparticles via a Semi-Continuous Soup-Free Emulsion Polymerization

Abstract

Hybrid nanoparticles were prepared by direct polymerization of methyl methacrylate, vinyl acetate, and styrene monomers onto the unmodified hydrophilic surfaces of 33 nm silica nanoparticles in a semi-continuous soap-free emulsion polymerization at a monomer starved condition. The polymerization was initiated by potassium persulfate with constant monomer feed at 0.01, 0.02, or 0.04 mL/min. The growth of the core-shell nanoparticles were measured by a laser particle size analyzer. FT-IR spectra analysis confirmed the hybrid structures of the synthesized nanoparticles. SEM images and size exclusion chromatography (SEC) results indicated regular core-shell microsphere structures. The hybrid nanoparticles increased in monodispersity and size over 100 nm with the reaction. However, SiO2/polystyrene (PS) nanoparticles grew much faster compared with SiO2/polymethyl methacrylate (PMMA) and SiO2/polyvinyl acetate (PVAC). There was particle coagulation, about 12 SiO2/PS particles aggregating to one, in the early stage of the seeded process. In addition, PS secondary particles were formed before the particle coagulation, and then merged with the SiO2/PS nanoparticles in the particle coagulation. The formation of SiO2/polymer hybrid nanoparticles depended on the hydrophilic characteristics of the polymer, and the size of silica seeds.