Motional heterogeneity of segmented polyurethane–polymethacrylate mixtures: an influence of functional groups concentration

The motional heterogeneity in the polymer mixtures of segmented polyether polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups was studied by the electron spin resonance (ESR)—spin probe and spin label methods. Pure polymer components containing varying amounts of functional groups and their 1:1 mass ratio mixtures have been analysed. The results of motional heterogeneity and polymer interaction were complemented with the glass transition temperatures, structural and morphological characteristics. Spin probed PU/PM mixtures indicate that the probe motion and the phase separation deduced from the temperature-dependent ESR spectra are sensitive to a free volume determined by the polymer–polymer interactions. The interaction between the two components in PU/PM mixture with the highest functional groups concentration disorganizes hard segment domains with spherulitic character at the microscopic level as compared with the ordered hard phase in the corresponding pure PU sample. The influence of PU hard and soft segments on the motional dynamics of PM chains is analysed from the ESR spectra of spin labelled PM chains in the mixtures with unlabelled PU components. The fractional amount of the PM fast motion depends on the temperature and concentration of functional groups.