Thermosensitive Hairy Hybrid Nanoparticles Synthesized by Surface-Initiated Atom Transfer Radical Polymerization

• Published in: Langmuir Vol. 22; no. 7; pp. 3344 - 3351
• Main Authors: Li, Dejin, Jones, Gregory L, Dunlap, John R, Hua, Fengjun, Zhao, Bin
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 28.03.2006
• Subjects: Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Physical and chemical studies. Granulometry. Electrokinetic phenomena; Scanning electron microscopy; Nanoparticle; Light scattering; Ethylene; Thermogravimetry; Polymerization; Polymer; NMR spectrometry; Silica; Phase transitions; Gel permeation chromatography; Cloud point; Free water; Synthesis; Dynamics; Glycol
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la053103+

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 Stöber 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 (<2 °C).