Title: How Do Ionic Liquids “Fold” Ionenes? Computational and Experimental Analysis of Imidazolium Polymers Based on Ether and Alkyl Chain Variations Dissolved in an Ionic Liquid

Abstract

Molecular dynamics (MD) simulations and complementary experiments are used here to understand the inter- and intramolecular structure and conformational properties of ionenes (i.e., cationic polymers formed from condensation reactions) dissolved in an ionic liquid (IL), 1-ethyl-3-methylimidazolium bistriflimide [C₂mim⁺][Tf₂N^-]. The simulated structural properties are benchmarked against experimental analyses of these same polymers, mainly using dynamic light scattering (DLS) experiments. Four different imidazolium ionenes are considered, corresponding to variations in the chemistry and structure of the repeat units including: (1) poly (decylimidazolium) (PD₁₀); (2) poly (tetraethyleneglycolimidazolium) (PE₁₀); (3) alternating copolymer (P(ED)₅); and (4) a block copolymer (PE₅D₅). Detailed computational analyses of the polymer structure and conformational properties were performed, including the radius of gyration, end-to-end distance, torsional distributions, and site-site and spatial distribution functions. Overall, there is a competition between intramolecular associations between the imidazolium groups and the ether sites in the polymers versus the intermolecular interactions of the polymer imidazolium groups with the surrounding anion molecules. The polymer with only ether linkages (PE₁₀) results in the most intramolecular interactions, leading to significant coiling behavior and chain contraction. These strong interactions reduce chain flexibility, but they also result in much more linear chain configurations and alignment of the imidazolium groups. The polymermore » structure is strongly affected as the concentration of alkyl groups is increased, and we find that the polymer architecture (alternating versus block copolymer) also has an important influence. Furthermore, these detailed observations are important for understanding the connection between the molecular design of imidazolium polymers and their emergent structural properties, which could lead to unique opportunities for creating polymer composites.« less

Authors:

Sappidi, Praveenkumar ^[1]; Liu, Xiaoyang  ^[1];

• Search DOE PAGES for author "Liu, Xiaoyang"
• Search DOE PAGES for ORCID "0000-0002-8172-6756"

O’Harra, Kathryn E. ^[1]; Bara, Jason E. ^[1]; Turner, C. Heath  ^[1]

• Search DOE PAGES for author "Turner, C. Heath"
• Search DOE PAGES for ORCID "0000-0002-5707-9480"

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+ Show Author Affiliations

1. Univ. of Alabama, Tuscaloosa, AL (United States)

Publication Date:

Mon Jan 25 00:00:00 EST 2021

Research Org.:

Univ. of Alabama, Tuscaloosa, AL (United States)

Sponsoring Org.:

USDOE Office of Science (SC)

Contributing Org.:

Univ. of Alabama, Tuscaloosa, AL (United States)

OSTI Identifier:

1759985

Grant/Contract Number:  

SC0020282

Resource Type:

Accepted Manuscript

Journal Name:

Macromolecules

Additional Journal Information:

Journal Volume: 54; Journal Issue: 4; Journal ID: ISSN 0024-9297

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Imidazolium; ionic liquid; ionene; radius of gyration; molecular dynamics