Infrared spectroscopic studies of polymer transitions. III. Effects of sodium ion on glass transitions in styrene-based ionomers

The glass transition in styrene-based ionomers was investigated by means of infrared spectroscopy and differential scanning calorimetry (DSC). Transition temperatures were determined from the temperature dependence of the peak absorbances of the 1700 and 1745 cm^?1 bands. These transition temperatures agreed with glass transition temperatures (T_g) determined by DSC. With increasing degree of ionization, T_g and the enthalpy ΔH of the residual intermolecular hydrogen bonding increased. The values of T_g obtained were analyzed by the theory of Fox and Loshaek for the effect of crosslinks. It is concluded that sodium ions probably from ionic domains and act as crosslinks to reinforce the residual hydrogen bonding and may increase T_g. The absorbance at 1560 cm^?1 (ν_COO^?) did not change at T_g. This suggests that the glass transition observed here is not due to the onset of the mobility in ionic domains, as has been proposed for ethylene-based ionomers on the basis of dielectric measurements.