Transition from star-like to crew-cut micelles induced by UV radiation

In the present article, the effect of UV on PS-b-PMMA micelles in solution is discussed. Micellar solutions of the amphiphilic poly(styrene-b-methylmethacrylate) block copolymer in selective solvent (methanol for the PMMA block) were exposed to UV radiation, which has simultaneously led to cross linking of the micellar core (PS) and degradation of the micellar corona (PMMA). The kinetics of such process were investigated in situ by means of dynamic light scattering, allowing the measurement of hydrodynamic radius as a function of UV exposure time. Results indicate that the size of micelles has decreased with UV exposure time down to a minimum value. Such reduced size resulted from PMMA degradation, which later promoted aggregation and coagulation because the micellar core was no longer well protected by PMMA. Addition of good solvent for both blocks (toluene) to non-UV exposed micelles has led to core swelling (PS) and, ultimately, system disassembly (free copolymer chain). The effect of adding toluene on the UV-exposed micelles has only caused core swelling as a consequence of the PS cross-linking.