We perform a comprehensive set of coarse-grained molecular dynamics simulations of ionomer melts with varying polymer architectures and compare the results to experiments in order to understand ionic aggregation on a molecular level. The model ionomers contain periodically or randomly spaced charged beads, placed either within or pendant to the polymer backbone, with the counterions treated explicitly. The ionic aggregate structure was determined as a function of the spacing of charged beads and also depends on whether the charged beads are in the polymer backbone or pendant to the backbone. The low wavevector ionomer peak in the counterion scattering is observed for all systems, and it is sharpest for ionomers with periodically spaced pendant charged beads with a large spacing between charged beads. Changing to a random or a shorter spacing moves the peak to lower wavevector. We present new experimental X-ray scattering data on Na(+)-neutralized poly(ethylene-co-acrylic acid) ionomers that show the same two trends in the ionomer peak, for similarly structured ionomers. The order within and between aggregates, and how this relates to various models used to fit the ionomer peak, is quantified and discussed.

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.

The room temperature morphologies of twelve precise copolymers based on polyethylene (PE) were studied by solid-state 13 C NMR, DSC, and X-ray scattering. These copolymers feature carboxylic acid, phosphonic acid or 1-methylimidazolium bromide pendants on exactly every 9th, 15th or 21st carbon atom along the linear PE chain. The morphologies were categorized by the arrangement of the acid or ionic aggregates into liquid-like, layered, or cubic morphologies. The liquid-like morphology is characterized by an amorphous PE matrix and liquid-like packing of the aggregates, wherein the interaggregate spacing increases with both the PE segment length and the pendant size. The layered morphologies typically have a semicrystalline PE matrix and upon stretching become highly anisotropic. Notably, the orientation of the aggregates and the PE crystallites relative to the stretch direction depends on whether the morphology is dominated by PE crystallization, as found for acrylic acid (AA) and phosphonic acid (PA) copolymers, or by the strong ionic aggregates, as found for the 1-methylimidazolium bromide (ImBr) copolymers. Cubic morphologies in these precise copolymers require geminal substitution, PA pendants, and sufficiently long PE segments to allow the aggregates to order. These precise copolymers provide an unprecedented array of morphologies that enable correlations between chemical structure and nanoscale morphologies.

Designing acid-and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly-(ethylene-co-acrylic acid) copolymer and ionomer melts.Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. In these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). The modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter-and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. This direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.