We report on interpolyelectrolyte complexes (IPECs) formed by micelles of ionic amphiphilic diblock copolymers with polyisobutylene (PIB) and poly(sodium methacrylate) (PMANa) blocks interacting with quaternized poly(4-vinylpyridine) (P4VPQ). The interpolyelectrolyte complexation was followed by turbidimetry and small angle neutron scattering (SANS). The data obtained by means of a combination of SANS, dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryo-TEM) provide evidence on the core-shell-corona structure of the complex species with the shell assembled from fragments of electrostatically bound PMANa and quaternized P4VPQ fragments, original PIBx-b-PMAAy micelles apparently playing a lyophilizing part. The complex formation is followed by potentiometric titration as well. This process is initially kinetically controlled. In the second step larger aggregates rearrange in favor of smaller complexes with core-shell-corona structure, which are thermodynamically more stable. An increase in ionic strength of the solution results in dissociation of the complex species as proven by SANS and analytical ultracentrifugation (AUC). This process begins at the certain threshold ionic strength and proceeds via a salt-induced gradual release of chains of the cationic polyectrolyte from the complex species.

Ionic amphiphilic diblock copolymer polyisobutylene-block-poly(methacrylic acid) (PIBx-b-PMAAy), with various lengths of nonpolar (x=25-75) and polyelectrolyte (y=170-2600) blocks, spontaneously dissolve in aqueous media at pH>4, generating macromolecular assemblies, the aggregation number of which depends on external stimuli (pH and ionic strength). Spherical micellar morphology with a compact core formed by the PIB blocks and a swollen corona built up from the PMAA blocks was deduced by cryogenic transmission electron microscopy. The micelles were further characterized by means of dynamic and static light scattering as well as small-angle neutron scattering. The critical micellization concentration, estimated by means of fluorescence spectroscopy with the use of pyrene as a polarity probe, is decisively determined by the length of the PIB block and is insensitive to changes in the length of the PMAA block.