  We have linked the structural and dynamic properties in aqueous solution of
amphiphilic charged diblock copolymers poly(butyl acrylate)-b-poly(acrylic
acid), PBA-b-PAA, synthesized by controlled radical polymerization, with the
physico-chemical characteristics of the samples. Despite product imperfections,
the samples self-assemble in melt and aqueous solutions as predicted by
monodisperse microphase separation theory. However, the PBA core are abnormally
large; the swelling of PBA cores is not due to AA (the Flory parameter
chiPBA/PAA, determined at 0.25, means strong segregation), but to h-PBA
homopolymers (content determined by Liquid Chromatography at the Point of
Exclusion and Adsorption Transition LC-PEAT). Beside the dominant population of
micelles detected by scattering experiments, capillary electrophoresis CE
analysis permitted detection of two other populations, one of h-PAA, and the
other of free PBA-b-PAA chains, that have very short PBA blocks and never
self-assemble. Despite the presence of these free unimers, the self-assembly in
solution was found out of equilibrium: the aggregation state is history
dependant and no unimer exchange between micelles occurs over months
(time-evolution SANS). The high PBA/water interfacial tension, measured at 20
mN/m, prohibits unimer exchange between micelles. PBA-b-PAA solution systems
are neither at thermal equilibrium nor completely frozen systems: internal
fractionation of individual aggregates can occur.
