Motional heterogeneity in poly(ether-block-amide) copolymers as revealed by solid-state NMR

An insight into the motional heterogeneity of a series of poly(ether-block-amide) copolymers is presented and discussed in terms of its NMR fingerprints dependent on a content and length of hard and soft segments and a microphase-separated morphology. Local-field dipolar spectra carry a straightforward signature of microphase-separated morphology endowed with a strong mobility gradient. The dipolar features of the poly(tetramethylene glycol) (PTMG) and polyamide-12 (PA) components, besides visualizing the presence of separated PTMG and PA phases, also give evidence for the presence of the dynamic heterogeneity of each component. H-1 MAS spectra provide an another fingerprint of phase-separated systems. Although such spectra roughly show increasing line broadening at higher PA/PTMG ratio, they are mainly sensitive to the presence of the most mobile fragments and may give a distorted vision of intrinsic mobility of the soft component in the presence of its dynamic heterogeneity. C-13 spectra bearing proton-carbon J-coupling features appear to be more sensitive to the length of the soft blocks and seem to bring a proper visualization of their overall mobility. Special attention has been paid to characterize motional heterogeneity of the soft component by exploiting cross-polarization transfer efficiency combined with indirect T-2(H-1) relaxation measurements. The cross-polarization inversion experiments provide, from heteronuclear dipolar interaction perspective, a corroborating visualization of the extent of motional distribution of the PTMG component. The revealed fingerprints of the motional heterogeneity of the soft component and the ways exploited in this work for their retrieval might be helpful for a better assessment of its role in the mechanical properties of thermoplastic elastomers.