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Langmuir 2006, 22, 3344-3351
Thermosensitive Hairy Hybrid Nanoparticles Synthesized by Surface-Initiated Atom Transfer Radical Polymerization Dejin Li,† Gregory L. Jones,‡ John R. Dunlap,‡ Fengjun Hua,† and Bin Zhao*,† Department of Chemistry, The UniVersity of Tennessee, KnoxVille, Tennessee 37996, and Program in Microscopy, The UniVersity of Tennessee, KnoxVille, Tennessee 37996 ReceiVed NoVember 16, 2005. In Final Form: January 27, 2006 This article reports on the synthesis of thermosensitive polymer brushes on silica nanoparticles by atom transfer radical polymerization (ATRP) and the study of thermo-induced phase transitions in water. Silica nanoparticles were prepared by the Sto¨ber process and the surface was functionalized by an ATRP initiator. Surface-initiated ATRPs of methoxydi(ethylene glycol) methacrylate (DEGMMA) and methoxytri(ethylene glycol) methacrylate (TEGMMA) were carried out in THF at 40 °C in the presence of a free initiator, benzyl 2-bromoisobutyrate. The polymerizations were monitored by 1H NMR spectroscopy and gel permeation chromatography. The hairy hybrid nanoparticles were characterized by thermogravimetric analysis and scanning electron microscopy, and the thermoresponsive properties were investigated by variable temperature 1H NMR spectroscopy and dynamic light scattering. The cloud points of free poly(DEGMMA) and poly(TEGMMA) in water were around 25 and 48 °C, respectively. The thermo-induced phase transitions of polymer brushes on silica nanoparticles began at a lower temperature and continued over a broader range (4-10 °C) than those of free polymers in water (
