An Electron Spin Resonance Study Comparing Nanometer–Nanosecond Dynamics in Diblock Copolymers and Their Poly(methyl Methacrylate) Binary Blends

Block copolymers are a class of materials that are particularly interesting with respect to their capability to self-assemble in ordered structures. In this context, the coupling between environment and dynamics is particularly relevant given that movements at the molecular level influence various properties of macromolecules. Mixing the polymer with a second macromolecule appears to be an easy method for studying these relationships. In this work, we studied blends of poly(methyl methacrylate) (PMMA) and a block copolymer composed of PMMA as the first block and poly(3-methyl-4-[6-(methylacryloyloxy)-hexyloxy]-4′-pentyloxy azobenzene) as the second block. The relaxational properties of these blends were investigated via electron spin resonance (ESR) spectroscopy, which is sensitive to nanometric length scales. The results of the investigations on the blends were related to the dynamic behavior of the copolymers. At the nanoscale, the study revealed the presence of heterogeneities, with slow and fast dynamics available for molecular reorientation, which are further modulated by the ability of the block copolymers to form supramolecular structures. For blends, the heterogeneities at the nanoscale were still detected. However, it was observed that the presence of the PMMA as a major component of the blends modified their dynamic behavior.