Conformational analysis of poly(MDI-butandiol) hard segment in polyurethane elastomers

Abstract

As part of our study of the structure of the hard segments of polyurethane elastomers, we have used conformational analysis to predict the conformation of the polyurethane chain formed from diphenylmethane 4,4′-diisocyanate (MDI), with butandiol as the chain extender. X-ray diffraction indicates the chain conformation is highly extended in the solid state, with a monomer repeat of 18.95 Å. The chain conformation can be predicted from the interaction between the large contiguous groups. Semiempirical and CNDO/2 molecular orbital calculations have been used to investigate the phenyl-phenyl, phenyl-urethane, and urethane-butandiol interactions. Minimum energy for the diphenyl-methane section occurs for a CCH 2C bridge angle of θ = 110°. However, the more likely conformation in the polymer is probably that at the subsidiary minimum at θ = 118°, in which the phenyl rings are mutually perpendicular, which is comparable to the conformation seen for model compounds. For the phenyl-urethane interactions the energy minimum is at ч = ±90°, with the combination (ч 1, ч 2) = (−90°, +90°) leading to the necessary extended conformation. Calculations for the butandiol segment favour an all- trans conformation which is coplanar with the urethane groups. The predicted conformation of the polymer chain has a fibre repeat which matches the observed value, and this cannot be attained if the butandiol unit contains any gauche bonds. Model compounds show large variations for the phenyl-urethane conformation from the predicted minimum at ч = ±90°, indicating the importance of intermolecular stacking forces in determining the polymer conformation. However, provided the adjacent butandiol and urethane groups are coplanar, the fibre repeat is relatively insensitive to variations of ч.