Structure of poly(vinyl alcohol)‐iodine complex formed in the amorphous phase of poly(vinyl alcohol) films

The effect of syndiotactivity of poly(vinyl alcohol) (PVA) both on the formation and thermal stability of the complex formed in the amorphous phase of PVA films is investigated, and then a model of the complex is presented. The amount of the complex formed in syndiotacticity-rich PVA is much larger than that formed in atactic PVA under a given iodine-soaking condition, and the former complex has a higher thermal stability in the soaking solution than the latter. The complex formed in the amorphous phase is proposed to have such a structure as that in which a linear polyiodine I5− or I5− with a 3.1 A˚ periodicity is enveloped by four PVA segments of syndiotactic configuration with extended conformation. In this model, these four PVA chains participating in a complex are supposed to be fixed by interchain hydrogen bonds. The observed X-ray meridional intensity curve of iodinated PVA film can be explained by a series of two I5−. © 1993 John Wiley & Sons, Inc.