Hydrogen Bonding in Polyurethanes: Preliminary Results of Simultaneous DSC-FTIR (Differential Scanning Calorimeter-Fourier Transform Infrared Spectroscopy) Experiments

摘要

The hydrogen bonding behavior of segmented polyurethane elastomers and model hard segment compounds has been examined by performing simultaneous Differential Scanning Calorimeter (DSC) and Fourier Transform Infrared Spectroscopy (FTIR) measurements. In model hard segments of 4,4'-diphenylmethane diisocyanate (MDI) extended with (2,2,3,3-d4) butanediol (BDO), and 2,4-toluenediisocyanate also chain extended with BDO, the spectra show a linear decrease in the apparent degree of hydrogen bonding over most of the temperature range. In the case of MDI-BDO, there is thus no clear correlation between DSC multiple endotherms and the degree of hydrogen bonding. Examination of an elastomer containing 70% bwt. of MDI/BDO hard segment and polyether soft segment however reveals a transition in the degree of hydrogen bonding coincident with an endotherm whose origin has been previously ascribed to the onset of a microphase mixing transition. This result clearly demonstrates that thermally induced morphological changes can affect markedly the hydrogen bonding behavior of polyurethanes. The study also illustrates that chemical changes occur during a typical DSC thermogram. In particular, reversal of the polyurethane reaction equilibrium is evidenced by emergence of an isocyanate absorbance band at high temperatures for all materials.