The micelle formation of five poly(2‐oxazoline) diblock, triblock and gradient copolymers in water was investigated using fluorescence correlation spectroscopy. The polymers were synthesized by consecutive or simultaneous living cationic polymerization of 2‐methyl‐2‐oxazoline for the hydrophilic and 2‐nonyl‐2‐oxazoline for the hydrophobic polymer segments. Fractions of the polymers were fluorescence‐labeled at the polymer termini with TRITC for the FCS measurements. The hydrodynamic radii of solubilized polymer unimers and of the aggregates (micelles) were determined in a concentration range of 10−8–10−3 M and were found to depend in a characteristic way on the polymer architecture.
Amphiphilic poly(2‐alkyl‐2‐oxazoline) diblock copolymers of 2‐methyl‐2‐oxazoline (MOx) building the hydrophilic block and either 2‐nonyl‐2‐oxazoline (NOx) for the hydrophobic or 2‐(1H,1H′,2H,2H′‐perfluorohexyl)‐2‐oxazoline (FOx) for the fluorophilic block were synthesized by sequential living cationic polymerization. The polymer amphiphiles form core/shell micelles in aqueous solution as evidenced using small‐angle neutron scattering (SANS). Whereas the diblock copolymer micelles with a hydrophobic NOxn block are spherical, the micelles with the fluorophilic FOxn are slightly elongated, as observed by SANS and TEM. In water, the micelles with fluorophilic and lipophilic cores do not mix, but coexist.
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