Synthesis and nanostructure of strong polyelectrolyte brushes in amphiphilic diblock copolymer monolayers on a water surface.

We synthesized an ionic amphiphilic diblock copolymer, poly(hydrogenated isoprene)-b-poly(styrenesulfonic acid) (PIp-h2-b-PSS), by living anionic polymerization, and the nanostructure of its monolayer spread on a water surface was directly investigated by the in situ X-ray reflectivity technique. The monolayer of the diblock copolymer on a water surface had a smooth hydrophobic PIp-h2 layer on water and a "carpet"/polymer brush double layer in a hydrophilic sodium polystyrene sulfonate (PSSNa) layer under the water. The surface pressure dependence and PSSNa chain length dependence of the PIp-h2 layer thickness and the brush nanostructure were quantitatively studied. The effect of salt concentration in the subphase was also investigated in aqueous solutions containing 0-2 M NaCl. The salt effect on monolayer structure occurred at around 0.2 M. The thickness of the PSS brush layer decreased at salt concentrations above 0.2 M, while no structural change was observed below 0.2 M. This critical salt concentration is thought to be related to the balance of ionic concentrations inside the brush and in bulk solution.