A novel type of amphiphilic ionic copolymer comprising a hydrophilic poly(acrylic acid) (PAA) block and an amphiphilic poly(acrylic acid)-grad-poly(styrene) (PAA-grad-PS) copolymer block was synthesized using a one step direct nitroxide-mediated polymerization (NMP). A strong influence of the macroinitiator on the values of the reactivity ratios of the co-monomers is confirmed by ¹H NMR. The aggregation behaviour of the copolymers in the aqueous medium was studied by small-angle neutron scattering (SANS) and dynamic light scattering (DLS) and by transmission electron microscopy (TEM) in a wide range of pHs and ionic strengths. It has been demonstrated that PAA-b-(PAA-grad-PS) copolymers are soluble in alkaline water at room temperature without the special experimental procedures (addition of co-solvent, heating, etc.) that are usually required for solubilisation of classical PAA-b-PS diblock copolymers. The self-assembly of the PAA-b-(PAA-grad-PS) copolymers into nano-scale aggregates at low/moderate pH and/or high ionic strength was demonstrated by SANS and DLS experiments. The SANS spectra for the copolymer solution exhibit a correlation peak pointing to the formation of micelles with repulsive coronae. TEM images indicate that the micelles have an approximately spherical shape and exhibit a wide size distribution. Our results prove, that in contrast to “frozen” aggregates formed by PAA-b-PS copolymers in aqueous media, the micelles of PAA-b-(PAA-grad-PS) amphiphilic copolymers exhibit “dynamic” pH-responsive properties, i.e. they can reversibly change their aggregation number upon a variation in the pH or salinity of the solution.

This article details the preparation of hierarchically ordered microporous films using the so-called breath figure approach combined with the self-assembly of well-defined poly(n-butyl acrylate)-block-polystyrene or poly(tert-butyl acrylate)-block-polystyrene copolymers synthesized by nitroxide-mediated polymerization. The first level of organization was the hexagonal pattern of pores at the micrometre length scale leading to iridescence properties and surface hydrophobicity of the honeycomb structured films. Optical microscopy with the corresponding 2-Dimensional Fast Fourier Transform highlighted the ordering of the pores over a large scale (∼1 cm²). The second level of structuring was provided by the diblock copolymers chosen for their ability to self-assemble into ordered nanophases. The nanoscale morphology of both the honeycomb films and the corresponding thermally annealed continuous films was systematically investigated by atomic force microscopy (AFM) and small angle neutron scattering (SANS). The film characterization revealed a nanostructuration of the acrylate-based coil–coil diblock copolymer within the walls of the highly ordered microporous films obtained via a simple solvent evaporation method under humid atmosphere. The four synthesized diblock copolymers exhibited different macromolecular features with respect to the Flory–Huggins interaction parameter, the glass transition temperature of each block and the weight fraction of each monomer that influenced the quality of either the micropores structuration or the nanophase segregation.

We demonstrate the possibility of reversible pH-controlled sol–gel transition in aqueous solution of associating amphiphilic triblock copolymer poly(styrene-grad-acrylic acid)-b-poly(acrylic acid)-b-poly(styrene-grad-acrylic acid), (PS-grad-PAA)-b-PAA-b-(PS-grad-PAA), synthesized vianitroxide-mediated (NM) radical copolymerization. The presence of pH-sensitive co-monomer units of the acrylic acid in the terminal blocks ensures the dynamic nature of the styrene-rich hydrophobic nano-domains which are formed at low pH. At small polymer concentrations the association triggered by lowering the pH gives rise to flower-like micelles stabilized by partially ionized PAA coronae. The pH-controlled association was monitored by DLS-titration and manifested in the evolution of a correlation peak in the SANS spectra. The resulting copolymer aggregates were visualized by TEM, which confirmed the spherical shape of the dense styrene-rich domains. Above the micelle overlap concentration a decrease in pH provokes macroscopic gelation. Here the styrene-reach domains perform as cross-links in the transient network. The pH-triggered sol-to-gel transition is manifested in an abrupt and strong (up to 3 orders of magnitude) increase in the zero-shear viscosity and in a characteristic change in the frequency dependence of the storage and loss moduli. The discovered effect can be used for efficient pH-control of the rheological properties of aqueous solutions.