This study examined the effects of the sodium salts of aliphatic dicarboxylic acids (DCAs) on the dynamic mechanical properties and morphology of two sets of poly(styrene-co-sodium methacrylate) (MNa) and poly(styrene-co-sodium styrenesulfonate) (SNa) ionomers. When the DCA content was relatively low, the ionic moduli of the MNa and SNa ionomers increased but the matrix and cluster glass transition temperature (T g ) did not change significantly. The increasing ionic modulus was almost independent of the type of the ionic groups of the ionomer, and the chain length of DCAs. When a large amount of the sodium succinate (DCA4) was added to the MNa and SNa ionomers, the ionic moduli of the two ionomers increased strongly but the matrix and cluster T g 's increased slightly and significantly, respectively. In the case of sodium hexadecanedioate (DCA16), DCA16 increased the ionic moduli of the two ionomers. The addition of DCA16 changed the matrix and cluster T g 's of the MNa ionomer slightly, but decreased the cluster T g of the SNa ionomer significantly with no change in the matrix T g . In addition, the DCA-containing ionomers showed an X-ray diffraction peak indicating the presence of ordered domains of DCAs in the ionomers. Hence, DCA4 acts mainly as a reinforcing filler in MNa and SNa systems. In the case of DCA16, it initially behaved like a filler but also functioned as a preferential plasticizer for the clusters at high content.
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