Various Types of Hydrogen Bonds, Their Temperature Dependence and Water−Polymer Interaction in Hydrated Poly(Acrylic Acid) as Revealed by 1H Solid-State NMR Spectroscopy

Various types of hydrogen bonds, their temperature dependence and water−polymer interaction in hydrated poly(acrylic acid) (PAA) were systematically investigated using 1H CRAMPS solid-state NMR techniques in the temperature range from 25 to 110 °C. The 1H CRAMPS NMR methods are based on a recently developed continuous phase modulation technique for 1H−H homonuclear dipolar decoupling. The 1H CRAMPS experiments revealed four types of protons in hydrated PAA which are assigned to protons from the mutually hydrogen-bonded COOH groups (1), from the free COOH groups (2), from the COOH groups bounded with water or from water bounded with COOH groups which are undergoing fast chemical exchange mutually (3), and from main chain groups (4), respectively. Furthermore, we proposed double-quantum filtered and dipolar filtered 1H CRAMPS experiments to further assign the protons according to their dipolar coupling strength. In addition, high-resolution spin echo 1H CRAMPS experiments were further employed to accurately determine the chemical shift of these protons. These NMR techniques were also used to elucidate the molecular mobility of the different groups. It was found that dehydration in PAA promotes the formation of hydrogen bonds between COOH groups. Variable-temperature 1H CRAMPS experiments demonstrated that the dissociation of the hydrogen bonds between COOH groups occurs dramatically at lower temperature in hydrated PAA and slowly over a wide range of temperature in dehydrated PAA. It was also found that the dehydration of water bounded with COOH groups in hydrated PAA occurs significantly at high temperature. The NMR results were compared with previous work using DSC and other techniques. Besides undergoing fast chemical exchange, the adsorbed water was also demonstrated in proximity with the free COOH groups and far from the hydrogen bonds between COOH groups by using two-dimensional 1H−1H spin-exchange NMR experiments.