High-Strength Heat-Elongated Thermoplastic Polyurethane Elastomer Consisting of a Stacked Domain Structure.

We found that a high-strength elastomer was obtained by the heat elongation of a thermoplastic polyurethane (TPU) film consisting of a high content of crystalline hard segments (HS). The stress upturn continuously increased with the elongation ratio without a decrease in the strain recovery by heat elongation, i.e., the stress at break of a quenched TPU film was increased from 55 to 136 MPa by heat elongation at an elongation ratio of 300%. The results of small-angle X-ray scattering, DSC, and AFM observations revealed that: (1) anisotropically shaped HS domains were stacked at a nanometer scale and the longer direction of the HS domains was arranged perpendicular to the elongated direction due to the heat elongation, (2) the densification of the HS domains increased with increases in the elongation ratio without a significant increase in the crystallinity, and (3) the stacked domain structure remained during the stretching at 23 °C. Thus, the strengthening of the elongated TPU might be attributed to the densification of the HS domains in the stacked structure, which prevents the fracture of the HS domains during the stretching.