Nanoscale morphology in precisely sequenced poly(ethylene-co-acrylic acid) zinc ionomers

The morphology of a series of linear poly(ethylene-co-acrylic acid) zinc-neutralized ionomers with either precisely or randomly spaced acid groups was investigated using X-ray scattering, differential scanning calorimetry (DSC), and scanning transmission electron microscopy (STEM). Scattering from semicrystalline, precise ionomers has contributions from acid layers associated with the crystallites and ionic aggregates dispersed in the amorphous phase. The precisely controlled acid spacing in these ionomers reduces the polydispersity in the aggregate correlation length and yields more intense, well-defined scattering peaks. Remarkably, the ionic aggregates in an amorphous, precise ionomer with 22 mol % acid and 66% neutralization adopt a cubic lattice; this is the first report of ionic aggregate self-assembly onto a lattice in an ionomer with an all-carbon backbone. Aggregate size is insensitive to acid content or neutralization level. As the acid content increases from 9.5 to 22 mol % at approximately 75% neutralization, the number density of aggregates increases by approximately 5 times, suggesting that the ionic aggregates become less ionic with increasing acid content.