Synthesis of Polymeric Nanoparticles by Cross-Linking Copolymerization

Abstract

Soluble cross-linked nanoparticles were prepared by free radical copolymerization of styrene (ST, M1) and ethylene glycol dimethacrylate (EGDM, M2) monomers in homogeneous solution. Spherical nanoparticles were obtained in the early stage of polymerization, and no gelation occurred up to 66% of yield. The isolated particles are decorated with pendant vinyl groups that are target for further polymerization. The molar feed ratio was ST/EGDM = 5/5, the monomer concentration 0.556 mol/dm3 and the initiator concentration 5 mol %. It was found that as the conversion increased, the ratio of pendant vinyl groups reached a maximum value; however, the size of nanoparticles continued to increase with the reaction time. The molecular weight distributions were monomodal at short reaction times (30 and 60 min), however, at longer reaction times (90, 120, and 180 min) these became multimodal. This was caused by intraparticle reactions (branching and cross-linking) and possibly also by interparticle reactions (coupling). The reactive vinyl groups were detected by nuclear magnetic resonance spectroscopy (NMR). The size of nanoparticles in swollen state was determined by dynamic laser light scattering (DLS) method and in dried form by scanning electron microscopy (SEM). Molecular weight and distributions were measured by gel permeation chromatography (GPC).