Moving-window two-dimensional correlation infrared spectroscopy study on structural variations of partially hydrolyzed poly(vinyl alcohol)

In the present study, the molecular chain changes and structural transitions of partially hydrolyzed poly(vinyl alcohol) (PVA) having a 12 mol% acetate unit were analyzed by moving-window two-dimensional (MW2D) correlation infrared spectroscopy combined with differential scanning calorimetry and thermogravimetric analysis. The results show the glass-transition temperature (Tg ) of PVA is clearly distinguished by MW2D correlation infrared spectroscopy, and the acetate groups start to be eliminated around the melting temperature, whereas the free water molecules in PVA are eliminated above Tg. The correlation movements of the O–H stretching modes, including the free hydroxyl groups and the hydrogen bonds, are clearly determined using MW2D correlation infrared spectroscopy. The spectral variations in the C=O stretching region caused by the elimination of the acetate unit from polymer chains are also discussed on the basis of the results of the MW2D correlation analysis. Such results cannot be obtained by traditional infrared spectroscopy owing to the complex overlapping peaks.