Transverse Orientation of Acid Layers in the Crystallites of a Precise Polymer
Abstract
Recently we reported an unusual multilayered structure in a linear polyethylene containing precisely periodic carboxylic acid groups pendant to every 21st carbon atom (p21AA). Within the ordered domains, p21AA executes tight chain folds at the location of each acid group, and the chainfold surfaces participate in hydrogen bonds with adjacent fold surfaces to form acid-rich layers. In this work, we investigate the bulk morphologies of p21AA after isothermal crystallization and, using X-ray scattering and polarized optical microscopy, find p21AA to be semicrystalline. By analyzing X-ray peak widths, creating real-space models of lamellae, and performing in-situ X-ray scattering during tensile deformation, we find that, contrary to the typical structure of polymer crystallites, the polymer stems lie in the plane of the lamellae such that the acid layers are transverse (within 30° of orthogonal) to the crystallite plane. This surprising structure, not reported before to our knowledge, could be useful for designing semicrystalline membranes because, given the appropriate chemistry, layers of functional groups could provide pathways for small molecule, ion, or proton transport through crystallites. We expect this novel structure to be accessible in similarly designed crystallizable polymers that contain evenly spaced, moderately sized, associating side groups.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Science Foundation (NSF); Rachleff Scholars Program; E.I. DuPont de Nemours & Co.; The Dow Chemical Company; Northwestern University; USDOE Office of Science (SC)
- OSTI Identifier:
- 1423349
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 22; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 36 MATERIALS SCIENCE; Crystallization; Crystal structure; Layers; X-ray scattering; Polymers
Citation Formats
Trigg, Edward B., Middleton, L. Robert, Moed, Demi E., and Winey, Karen I. Transverse Orientation of Acid Layers in the Crystallites of a Precise Polymer. United States: N. p., 2017.
Web. doi:10.1021/acs.macromol.7b02094.
Trigg, Edward B., Middleton, L. Robert, Moed, Demi E., & Winey, Karen I. Transverse Orientation of Acid Layers in the Crystallites of a Precise Polymer. United States. https://doi.org/10.1021/acs.macromol.7b02094
Trigg, Edward B., Middleton, L. Robert, Moed, Demi E., and Winey, Karen I. Tue .
"Transverse Orientation of Acid Layers in the Crystallites of a Precise Polymer". United States. https://doi.org/10.1021/acs.macromol.7b02094. https://www.osti.gov/servlets/purl/1423349.
@article{osti_1423349,
title = {Transverse Orientation of Acid Layers in the Crystallites of a Precise Polymer},
author = {Trigg, Edward B. and Middleton, L. Robert and Moed, Demi E. and Winey, Karen I.},
abstractNote = {Recently we reported an unusual multilayered structure in a linear polyethylene containing precisely periodic carboxylic acid groups pendant to every 21st carbon atom (p21AA). Within the ordered domains, p21AA executes tight chain folds at the location of each acid group, and the chainfold surfaces participate in hydrogen bonds with adjacent fold surfaces to form acid-rich layers. In this work, we investigate the bulk morphologies of p21AA after isothermal crystallization and, using X-ray scattering and polarized optical microscopy, find p21AA to be semicrystalline. By analyzing X-ray peak widths, creating real-space models of lamellae, and performing in-situ X-ray scattering during tensile deformation, we find that, contrary to the typical structure of polymer crystallites, the polymer stems lie in the plane of the lamellae such that the acid layers are transverse (within 30° of orthogonal) to the crystallite plane. This surprising structure, not reported before to our knowledge, could be useful for designing semicrystalline membranes because, given the appropriate chemistry, layers of functional groups could provide pathways for small molecule, ion, or proton transport through crystallites. We expect this novel structure to be accessible in similarly designed crystallizable polymers that contain evenly spaced, moderately sized, associating side groups.},
doi = {10.1021/acs.macromol.7b02094},
journal = {Macromolecules},
number = 22,
volume = 50,
place = {United States},
year = {Tue Nov 14 00:00:00 EST 2017},
month = {Tue Nov 14 00:00:00 EST 2017}
}
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