Abstract
We investigate a new series of precise ion-containing polyamide sulfonates (PASxLi), where a short polar block precisely alternates with a non-polar block of aliphatic carbons (x = 4, 5, 10, or 16) to form an alternating (AB)n multiblock architecture. The polar block includes a lithiated phenyl sulfonate in the polymer backbone. These PASxLi polymers were synthesized via polycondensation of diaminobenzenesulfonic acid and alkyl diacids (or alkyl diacyl chlorides) with x-carbons, containing amide bonds at the block linkages. The para- and meta-substituted diaminobenzene monomers led to polymer analogs denoted pPASxLi and mPASxLi, respectively. When x ≤ 10, the para-substituted diamine monomer yields multiblock copolymers of a higher degree of polymerization than the meta-substituted isomer, due to the greater electron-withdrawing effect of the meta-substituted monomer. The PASxLi polymers exhibit excellent thermal stability with less than 5% mass loss at 300 °C and the glass transition temperatures (Tg) decrease with increasing hydrocarbon block length (x). Using the random phase approximation, the Flory-Huggins interaction parameter (χ) is determined for pPAS10Li, and χ (260 °C) ∼ 2.92 reveals high incompatibility between the polar ionic and non-polar hydrocarbon blocks. The polymer with the longest hydrocarbon block, pPAS16Li, is semicrystalline and forms well-defined nanoscale layers with a spacing of ∼2.7 nm. Relative to previously studied polyester multiblock copolymers, the amide groups and aromatic rings permit the nanoscale layers to persist up to 250 °C and thus increase the stability range for ordered morphologies in precise ion-containing multiblock copolymers.
| Original language | English |
|---|---|
| Pages (from-to) | 5811-5819 |
| Number of pages | 9 |
| Journal | Polymer Chemistry |
| Volume | 13 |
| Issue number | 41 |
| DOIs | |
| State | Published - Aug 23 2022 |
| Externally published | Yes |
Funding
J. P. and K. I. W. acknowledge the support of funding by the NSF DMR (1904767). J. P. and K. I. W. also acknowledge NSF MRSEC (17-20530), NSF MRI (17-25969), and ARO DURIP grant (W911NF-17-1-0282) for the Dual Source and Environmental X-ray Scattering facility at the University of Pennsylvania. M. K. T. thanks the University of Maryland College Park for funding. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the US DOE Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the US DOE's National Nuclear Security Administration (contract no. DE-NA-0003525). The views expressed in the article do not necessarily represent the views of the US DOE or the US government.
| Funders | Funder number |
|---|---|
| NSF DMR | 1904767 |
| NSF MRI | 17-25969 |
| U.S. Department of Energy | |
| Army Research Office | W911NF-17-1-0282 |
| Army Research Office | |
| National Nuclear Security Administration | DE-NA-0003525 |
| National Nuclear Security Administration | |
| University of Maryland | |
| Materials Research Science and Engineering Center, Harvard University | 17-20530 |
| Materials Research Science and Engineering Center, Harvard University | |
| Government of South Australia |