WATER-INDUCED MICELLE FORMATION OF BLOCK COPOLY(OXYETHYLENE OXYPROPYLENE OXYETHYLENE) IN O-XYLENE

Static and dynamic light scattering, viscometry, NMR, and vapor pressure osmometry techniques have been employed to study the water-induced micellization behavior of poly(oxyethylene-oxypropylene-oxyethylene) block copolymer, Pluronic L64, in o-xylene solution. Results show that Pluronic L64 does not form polymolecular micelles in the absence of water or in the presence of a small amount of water (molar ratio water/EO < 0.15). Micelles, consisting of a PPO shell and a PEO and H2O core, are formed when the water to EO molar ratio (Z) in the micelle is greater than 0.2. For Z < 1.3, spherical micelles with an average hydrodynamic radius R(h) of Ca. 9.2 nm are formed, with R(h) almost independent of Z. For Z > 1.3, both the aggregation number and the hydrodynamic radius become dependent on the Z value, then the micelle shape could be nonspherical. As experimentally evidenced by NMR spectra, the solubilized water can be classified into bound water and free water. Most likely, water is not evenly distributed in the core, as the environments of EO units at different positions in the block copolymer are not identical.