Association behavior of star-shaped pH-responsive block copolymer: four-arm poly(ethylene oxide)-b-poly(methacrylic acid) in aqueous medium.

A four arm pH-responsive poly(ethylene oxide)-b-poly(methacrylic acid) block copolymer was synthesized by atom transfer radical polymerization technique. The conformation transition over the course of neutralization was investigated using a combination of potentiometric and conductometric titrations, dynamic and static light scattering, and transmission electron microscopy. The multiarm block copolymer existed as an extended unimer at high pH due to the negatively charged carboxylate groups and hydrophilic poly(ethylene oxide) segments. The block copolymers self-assembled into core-shell micelles and large spherical aggregates that flocculated at low degree of neutralization (alpha). Such behavior is controlled by the fine balance of electrostatic, hydrophobic, and hydrogen bond interactions. The hydrodynamic radius (R(h)) of the aggregates was approximately 84 nm at alpha of 0.3, and it decreased to 63 and 46 nm at alpha approximately 0.2 and 0.1, respectively, as a result of the reduced electrostatic interaction between ionized carboxylate groups. The thermodynamic parameters obtained from isothermal titration calorimetric technique in different salt concentrations indicated that the energy to extract a proton from a charged polyion was reduced by the addition of salt, which favors the neutralization process.