Strain-induced structural and dynamic changes in segmented polyurethane elastomers
作者：Wang, F. F.; Chen, S. L.; Wu, Q.; Zhang, R. C.*; Sun, P. C.*
關鍵字：Polyurethane, Elastomer, Strain-hardening, Mobility, Crystallization, Solid-state NMR
論文來源：期刊
具體來源：Polymer 2019, 163, 154–161.
發(fā)表時間：2019年
Polyurethane elastomers have been widely used in the industry and daily life due to their versatile physical and chemical properties. Therefore, a fundamental understanding of the structures and dynamics at a molecular level will provide piercing insights into the precise design and application of new polyurethane materials. In this study, we mainly focused on investigating the strain-induced structural and dynamic changes in a typical polyurethane elastomer composed of poly(epsilon-caprolactone) (PCL) and 4,4''''-diphenylmethylene diisocyanate (MDI) as the soft and hard segments, respectively. Obvious strain-hardening phenomenon was observed during the mechanical tensile test, and a systematic comparison was performed on the fractured and pristine samples. DSC results revealed that the crystallization of PCL chains was still going on after the sample was fractured, and the crystallite structures became stable after physical aging at 25 degrees C for two days. H-1 solid-state nuclear magnetic resonance (NMR) experiment was further employed to determine the fraction of mobile PCL chains that were converted to crystallites during stretching. Besides, the microphase separation was also significantly enhanced in the fractured sample. The mobility of amorphous PCL chains was largely reduced due to the strain-induced crystallization of nearby PCL segments, as revealed by the H-1 magic-sandwich echo (MSE) NMR experiments. H-1 multiple quantum (MQ) NMR experiments also quantitatively revealed the strain-induced orientation of amorphous PCL chains in the fractured sample, indicating that the PCL crystallites were acting as the physical cross-linkages to prevent the contraction of the elongated PCL chains when the sample is fractured.