Infrared and near-infrared spectral evidence for water clustering in highly hydrated poly(methyl methacrylate).

First, we developed quantitative analytical methods of water in poly(methyl methacrylate) (PMMA) in various hydrated states by utilizing the first combination and OH stretching bands of water at about 5240 and 3630 cm-1, respectively. Next, we investigated how the state of water depended on its quantity or the mole ratio of water to the CO (denoted as the H2O/CO ratio), which only interacts with water in PMMA, mainly on the basis of the band feature of the OH stretching bands. Below the H2O/CO ratio of 0.032, the contained water, which shows two clear bands at about 3630 and 3550 cm-1, is hydrogen-bonded to two C=O groups as C=O::H-O-H::O=C to form "the hydration core". The spectrum of the water that exceeds the ratio in question shows one broader band only, the frequency of which shifts downward with the increasing hydration. From detailed analysis of the behavior of the OH stretching and combination bands in relation to the H2O/CO ratio, we have concluded that the water that exceeds the hydration ratio becomes mobile to aggregate or "cluster" around hydrated sites rather than nonhydrated ones in the PMMA matrix, although the latter is much larger in population.