Phase-mixing and molecular dynamics in poly(urethane urea) elastomers by solid-state NMR

作者：Hu Weiguo^*; Hsieh Alex J

来源：Polymer, 2013, 54(22): 6218-6225.

DOI：10.1016/j.polymer.2013.09.010

• Poly(urethane urea)
• Nuclear magnetic resonance
• Molecular dynamics

The dynamical heterogeneity in a series of 4,4'-dicyclohexylmethane diisocyanate-diethyltoluenediamine-poly(tetramethylene oxide) based poly(urethane urea) (PUU) elastomers was studied by solid-state nuclear magnetic resonance (NMR) methods. Extensive phase mixing was evidenced by the H-1 wideline signal, which can be approximately fitted by a single exponential model. C-13 T-1 relaxation time measurements indicate that the hard segments (HS) exhibit some small-amplitude mobility, likely "activated" by neighboring soft segments (SS). Fitting of the time-domain wideline separation (TD-WISE) data was employed to characterize the extent of phase mixing, which revealed that a PUU elastomer contains four fractions: rigid-HS, mobile-HS, rigid-SS, and mobile-SS regions. For a variety of SS MWs, the dynamics and relative portions of rigid vs. mobile fractions among HS were substantially similar, while those for the SS exhibit large contrast. Furthermore, the dynamics in the rigid-SS fraction is at least an order of magnitude slower than that in mobile-SS. for all PUUs. Greater phase-mixing substantially lowers the SS mobility, facilitating SS to undergo glass transition at high strain rates, thus can be key to enhancing dynamic mechanical strengthening.

• 出版日期2013-10-18