Abstract
Neodymium(III) (Nd(III)) salts of poly(ethylene-co-5.4 mol% methacrylic acid) (EMAA) were synthesized in the neutralization range from 0 to 100%. The coordination structure, the formation and structure of ionic aggregates and their microphase separation were investigated. The infrared spectral results suggested that local environments around Nd(III) ions significantly change near 50% neutralization. Above this degree of neutralization, the X-ray scattering and visible spectral results indicated the presence of ionic aggregates. Interestingly, almost simultaneously with the ionic aggregation, a microphase separation of ionic aggregates from the polymer matrix (the formation of ionic cluster phase in Eisenberg’s terminology) was found to take place by dynamic mechanical and dielectric relaxational measurements. The activation energy for the α relaxation (340–420 kJ mol−1), which is attributed to the glass transition of the ionic cluster phase, and the melt flow rate revealed that the Nd(III) ionomers were densely cross-linked by either isolated or aggregated ions. The stiffness also indicated the existence of the densely cross-links, and the Nd(III) ionomers exhibited the higher stiffness compared with the monovalent and divalent salts of EMAA.
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