Moving-window two-dimensional correlation infrared spectroscopic study on the dissolution process of poly(vinyl alcohol)

In this paper, the dissolution process of fully hydrolyzed polyvinyl alcohol (PVA) was investigated by temperature–dependent Fourier transform infrared spectroscopy (FTIR) combined with moving-window two-dimensional (MW2D) correlation infrared spectroscopy (IR). The results show that the FTIR spectra of PVA in OH stretching and bending regions exceed the measuring range of the spectrometer because of the presence of abundant water. The OH stretching and bending peaks reveal that the water mainly diffuses into amorphous region below 45 °C, and water molecules mainly diffuse into crystalline region above 45 °C. The peak at 1141 cm–1 has ever been thought as the indication of crystallinity of PVA in solid state, but in solution, the peak does not decrease with the dissolution of crystalline region and finally increases when PVA is dissolved completely. The hydrogen bonds between hydroxyl groups in PVA chains are broken by water molecules but abundant new hydrogen bonds between hydroxyl groups in PVA chains and water molecules are formed during the dissolving process. In the 2D correlation analysis of the FTIR spectra, only the correlation movements of hydroxyl groups, including stretching and bending mode, can be observed. The correlation range and intensity are larger than that of PVA in solid state because the dissolution is the interaction process of water molecules diffusing into PVA chains.