We have studied the phase behavior of the poly(n-butyl
acrylate)-b-poly(acrylic acid) block copolymer in a mixture of two miscible
solvents, water and tetrahydrofuran (THF). The techniques used to examine the
different polymers, structures and phases formed in mixed solvents were static
and dynamic light scattering, small-angle neutron scattering, nuclear magnetic
resonance and fluorescence microscopy. By lowering the water/THF mixing ratio
X, the sequence unimers, micron-sized droplets, polymeric micelles was
observed. The transition between unimers and the micron-sized droplets occurred
at X = 0.75, whereas the microstructuration into core-shell polymeric micelles
was effective below X = 0.4. At intermediate mixing ratios, a coexistence
between the micron-sized droplets and the polymeric micelles was observed.
Combining the different aforementioned techniques, it was concluded that the
droplet dispersion resulted from a solvent partitioning that was induced by the
hydrophobic blocks. Comparison of poly(n-butyl acrylate) homopolymers and
poly(n-butyl acrylate)-b-poly(acrylic acid) block copolymers suggested that the
droplets were rich in THF and concentrated in copolymers and that they were
stabilized by the hydrophilic poly(acrylic acid) moieties.Comment: 11 pages, 12 figures, to appear in Macromolecule
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