Micelle Formation of a Rod−Coil Diblock Copolymer in a Solvent Selective for the Rod Block

Abstract

Aggregation of an amphiphilic rod−coil diblock copolymer, poly(n-hexyl isocyanate)-b-poly(ethylene glycol) (PHIC-b-PEG), in toluene, a selective solvent for the rodlike PHIC block, was studied using light scattering and polarized optical microscopy. Static and dynamic light scattering data indicate the formation of cylindrical micelles with a hydrodynamic radius of 279 nm in very dilute solutions (weight fraction of polymer, w, from 0.0002 to 0.008) at 25 °C. The cylindrical micelles were determined to be disklike (planar), 0.9 μm in diameter and 20 nm in thickness, based on a comparison between the experimental data and the theory of scattering and self-diffusion of ellipsoids. Planar aggregates are expected if nematic interactions of the coronal rod block are dominant. The aggregate size decreases with increasing temperature. The micelles were observed visually in solution with the help of a polarized optical microscope due to the optical anisotropy of the PHIC block. Disklike objects with diameters in the micron range were observed to undergo translational and rotational motion in and out of the focal plane of the microscope.