Microphase structure of polyurethane-polyurea copolymers as revealed by solid-state NMR: Effect of molecular architecture

H-1 spin-diffusion solid-state NMR, in combination with other techniques, was utilized to investigate the effect of molecular architecture, solubility parameter of hard and soft segments, and their length on the domain size, interphase thickness and degree of phase separation in polyurethane-ureas based on oligomeric 4,4'-diisicyanate diphenylmethane, methylene-bis-(2-chloroaniline) and polyols based on polyethylene oxide, polypropylene oxide and polybutadiene with different length. Polyurethane-ureas based on polyethylene oxide soft blocks did not form rigid domains as a result of absence of microphase separation. The domain sizes of the hard segments in polyurethane-ureas under study practically did not show any dependence on their composition, but interphase thicknesses are higher for systems based on polybutadiene soft blocks. This indicates that the degree of phase separation depends strongly not only on the binary thermodynamic interaction between hard and soft segments in polyurethane-ureas, but is also influenced by their molecular architectures in the experimental temperature range. (C) 2018 Elsevier Ltd. All rights reserved.