[en] radical polymerization ; atom transfer radical polymerization (ATRP) ; thermoplastic elastomer
[fr] nanostructured material ; self-assembly in bulk
[en] We investigate the microscopic morphology of thin films of symmetric triblock copolymers synthesized via a two-step “living” radical polymerization of n-butylacrylate and methyl methacrylate. These copolymers with low poly(methyl methacrylate) contents constitute a new class of potential thermoplastic elastomers with higher service temperature and oxidation resistance compared to conventional polydiene−polystyrene-based thermoplastic elastomers. The straightforward synthetic pathway allows for strict control of molecular weight, molecular-weight distribution, and composition. The presence in the copolymer of immiscible segments covalently bound to each other leads to phase separation on the nanometer scale. Regular organization of the phase-separated nanodomains is observed in real space by scanning force microscopy. The data point to a strong contrast in the local mechanical properties, corresponding to the microphase morphology. Cylinders of the minority phase are found to orient perpendicular to the surface, because of the surface energy difference between the constituents. Lamellae are also arranged perpendicular to the surface, in contrast to what is usually observed in block copolymers. This particular orientation is thought to result from the symmetric character of these triblock systems, with the outer blocks more polar than the central sequence.
Center for Education and Research on Macromolecules (CERM)
Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; the European Commission and the Government of the "Région Wallonne" (Project NOMAPOL-Objectif1-Hainaut) ; Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; IBM ; Elf Atochem