The pressure-induced structural changes of a block copolymer, poly(2-ethoxyethoxyethyl vinyl ether)-block-poly(2-hydroxyethyl vinyl ether) (pEOEOVE-b-pHOVE) in aqueous solutions, were studied by means of small-angle neutron scattering (SANS) and dynamic light scattering (DLS) from atmospheric pressure up to 400MPa. pEOEOVE-b-pHOVE formed a spherical micellar structure above 40°C due to poor solubility of pEOEOVE. Micellization phase diagram was determined by DLS, and a covex-upward pressure-temperature (P-T) phase diagram was obtained having a peak around (P,T)=(150MPa,48°C). The SANS curves at 50°C were analyzed as a function of P. The micellar core size decreased by pressurizing at low P’s (P150MPa) and then increased by further pressurizing (150MPa<P<400MPa). It was confirmed that the water volume fraction in the micellar core was larger at high P’s than that at low P’s even when the core sizes are the same at both pressure regions. This means that the temperature dependence of hydration is more selective at low pressures than at high pressures, in good accordance with our previous results on concentrated aqueous solutions of block copolymers [Phys. Rev. Lett.96, 048303 (2006)].

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