Graft copolymers having hydrophobic backbone and hydrophilic branches. XXIII. Particle size control of poly(ethylene glycol)-coated polystyrene nanoparticles prepared by macromonomer method

Monodisperse polymeric nanospheres, which consist of polystyrene cores and poly(ethylene glycol) (PEG) branches on their surfaces, were prepared by the dispersion copolymerization of styrene (St) with PEG macromonomers that had a methacryloyl (MMA-PEG) or p-vinylbenzyl (St-PEG) end group in various organic solvent/water media. Electron spectroscopy for chemical analysis (ESCA) of the nanosphere surfaces indicated that PEG macromonomer chains were favorably located on their surfaces. The morphologies of the nanospheres were observed via a scanning electron micrograph (SEM), and particle sizes were estimated by a submicron particle analyzer. When both the concentration of macromonomers and molecular weight were higher, small nanospheres in diameter were obtained. Larger nanospheres in diameter were obtained using macromonomers with low molecular weight at lower concentration. The functions that correlate the diameter (D_n) on different concentration units were D_n = KSt]^0.64MMA-PEG]^{−0.53±0.01}I]^−0.49 and D_n = KSt]^0.80St-PEG]^{−0.69±0.01}I]^−0.22, where I], St], MMA-PEG], and St-PEG] are initiator, styrene, MMA-PEG, and St-PEG macromonomer concentration in feed, respectively. When the reaction parameters such as the molecular weight of the macromonomers were properly chosen, the particle size could be controlled in a range from ca. 80 to 3100 nm. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2155–2166, 1999