Micellization behavior of complex comblike block copolymer architectures

Complex comblike block copolymers of various architectures containing polystyrene, PS, and polyisoprene, PI, or polybutadiene, PB, components were synthesized by anionic polymerization high-vacuum techniques and the macromonomer strategy. Their micellization behavior was studied in n-decane, a selective solvent for the PI or PB blocks, and in N,N′-dimethylacetamide, DMA, selective for the PS blocks. Utilizing static and dynamic light scattering techniques, parameters such as the aggregation number and the hydrodynamic radius were determined. On the basis of these results, structural parameters of the micelles, i.e., core and corona radii as well as core-corona interfacial area, were calculated. The thermal stability of the micelles was also examined in both selective solvents. The macromolecular architecture was found to have a considerable effect on the micellization behavior of the block copolymers.