Effect of metal cation type on the structure and properties of ethylene ionomers

Abstract Thermal properties by DSC, stiffness, melt viscosity, tensile properties, and dynamic mechanical properties were measured for the Na + , K + , Mg 2+ , Zn 2+ , Cu 2+ , Mn 2+ , and Co 2+ salts of poly(ethylene‐ co ‐methacrylic acid) (EMAA). The changes in the structure and properties with increasing neutralization are larger in the alkaline and alkaline earth metal salts than in the transition metal salts. The stiffness shows a maximum at 33% neutralization in both the alkaline and alkaline earth metal salts, while no maxima are found up to 60% neutralization in the transition metal salts. The microphase separation of salt group aggregates is observed in both the alkaline and alkaline earth metal salts, but is not seen in the transition metal salts. These differences were attributed to both the stronger ionic interactions and the larger number of carboxyl groups associated with the alkaline and alkaline earth metal salts in the ordered structure of ionic salt groups (ionic crystallites). The mechanical properties measured at low strain, such as stiffness and yield stress, strongly depend on the degree of the crystalline order of the ionic crystallites. The high‐strain properties, such as tensile strength and elongation at break, depend on the strength of the ionic interactions and the valence of the cation.