Large structures in diblock copolymer micellar solution

The association properties in water solution of poly(dimethylsiloxane)-b-poly(ethyleneoxide) diblock copolymer was investigated by static and dynamic light scattering in a wide range of concentrations and temperatures. The presence of a long hydrophilic poly(ethyleneoxide) (PEO) chain causes a weak tendency to microphase separation of the system which is responsible for some relevant effects. First of all we observe a late micellization process which is characterized by an unusually high value of the critical micellar concentration sccmc=0.007 g/cm3d and by an unusually small aggregation number s<6d of the generated micelles. Moreover, the composition of the highly hydrated micelles has been found to change sensitively with temperature. On increasing temperature dehydration of micelles has been observed together with a contemporaneous increase in the aggregation number, whereas the hydrodynamic radius remains constant in the whole range investigated. The long hydrophilic chains also stimulate an efficient entanglement process between micelles. The interpenetrating PEO chains belonging to different micelles causes the depletion of the solvent in the outer layer of micelles. The result is the formation, just after the micellization process takes place, of thermodynamically stable clusters of entangled micelles. These large structures, which are present in the system in small concentrations, maintain their structural properties unchanged in a wide range of concentrations and temperatures, and provide indirect evidence of a weak attractive component to the intermicellar interaction potential.