Light-scattering and viscometric results are presented from micellar solutions of (PI)2PS
(I2S) and (PS)2PI (S2I) three-miktoarm stars and a PSPI (SI) diblock copolymer in n-decane. The influence
of architecture on the micellization properties of simple graft copolymers is investigated by keeping the
overall molecular weights and compositions of the samples constant. All samples formed spherical micelles
in n-decane, a selective solvent for polyisoprene. Aggregation numbers were found to increase in the
order I2S < S2I < SI. Hydrodynamic radii of the micelles increased in the same order. The thickness of
the corona is determined by the length of the soluble blocks, which they were found to be stretched to
almost the same extent in all cases. The area of the core−corona interface per copolymer chain, A
c, depends
on the architecture of the molecule, and it is larger in the case of I2S micelles. In the case of S2I, larger
A
c values were found compared to the SI reference sample, indicating that the PS arms are arranged in
different ways in the two kinds of micelles. The presence of only one grafted chain per molecule can
change considerably the micellar characteristics of complex block copolymers. A simple scaling theory is
developed taking into account the free energy contributions from the core, the corona, and the interfacial
region of the micelle in the different cases. Theoretical predictions agree qualitatively with the
experimental results.
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