Role of Hydrogen Bonding on Nonlinear Mechano-Optical Behavior of l‑Phenylalanine-Based Poly(ester urea)s

The uniaxial mechano-optical behavior of a series of amorphous l-phenylalanine-based poly­(ester urea) (PEU) films was studied in the rubbery state. A custom, real-time measurement system was used to capture the true stress, true strain, and birefringence during deformation. When the materials were subjected to deformation at temperatures near the glass transition temperature (T_g), the photoelastic behavior was manifested by a small increase in birefringence with a significant increase in true stress. At temperatures above T_g, PEUs with a shorter diol chain length exhibited a liquid–liquid (T_ll) transition (rubbery–viscous transition) at about 1.06T_g (K) under the tested strain rate of 0.017 s^–1 (stretching speed of 20 mm/min), above which the material transforms from a heterogeneous “liquid of fixed structure” to a “true liquid” state. The initial photoelastic behavior disappears with increasing temperature, as the initial slope of the stress optical curves becomes temperature independent. Fourier transform infrared spectroscopy (FTIR) was used to study the effect of hydrogen bonding on the physical properties of PEUs as a function of temperature. The average strength of hydrogen bonding diminishes with increasing temperature. For PEUs with the longest diol chain length, the area associated with N–H stretching region exhibits a linear temperature dependence. However, a three-stage temperature dependence was observed for PEUs with shorter diol chain length. The presence of hydrogen bonding enhances the “stiff” segmental correlations between adjacent chains in the PEU structure. As a result, the photoelastic constant decreases with increasing hydrogen bonding strength.