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Title: Effect of Ionic Liquid Components on the Coil Dimensions of PEO

Abstract

Here, small-angle neutron scattering is used to measure the infinite dilution radius of gyration ($$R_{g,0}$$) for a range of molecular weights (10–250 kg/mol) of perdeuterated poly(ethylene oxide) (d-PEO) in various imidazolium-based ILs at 80 °C. The Flory exponents ($$\nu$$) evaluated in the ILs studied (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFSI]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4])) lie between 0.58 and 0.60, indicating good solvent behavior. The coil dimensions of d-PEO increase on increasing the alkyl chain length of the cation and on decreasing the anion basicity. A more pronounced effect on coil dimensions is observed upon altering the anion, compared to the dependence on cation alkyl chain length. The temperature dependence of $$R_{g,0}$$ is found to be moderate in 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), where the coil size decreases upon increasing the temperature from 80 to 135 °C. Addition of up to 10 wt % of a salt, lithium bis(trifluoromethylsulfonyl)imide, to mixtures of d-PEO and [BMIM][TFSI] has no significant effect on $$R_{g,0}$$. These results are discussed in terms of the relative interactions among PEO, the cation, and the anion.

Authors:
 [1]; ORCiD logo [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF); Northwestern University; E.I. DuPont de Nemours & Co.; The Dow Chemical Company; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1523530
Grant/Contract Number:  
AC02-06CH11357; 0960140
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 8; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Salts; Anions; Solvents; Cations; Polymers

Citation Formats

Kharel, Aakriti, and Lodge, Timothy P. Effect of Ionic Liquid Components on the Coil Dimensions of PEO. United States: N. p., 2019. Web. doi:10.1021/acs.macromol.9b00354.
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Kharel, Aakriti, & Lodge, Timothy P. Effect of Ionic Liquid Components on the Coil Dimensions of PEO. United States. https://doi.org/10.1021/acs.macromol.9b00354
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Kharel, Aakriti, and Lodge, Timothy P. Fri . "Effect of Ionic Liquid Components on the Coil Dimensions of PEO". United States. https://doi.org/10.1021/acs.macromol.9b00354. https://www.osti.gov/servlets/purl/1523530.
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@article{osti_1523530,
title = {Effect of Ionic Liquid Components on the Coil Dimensions of PEO},
author = {Kharel, Aakriti and Lodge, Timothy P.},
abstractNote = {Here, small-angle neutron scattering is used to measure the infinite dilution radius of gyration ($R_{g,0}$) for a range of molecular weights (10–250 kg/mol) of perdeuterated poly(ethylene oxide) (d-PEO) in various imidazolium-based ILs at 80 °C. The Flory exponents ($\nu$) evaluated in the ILs studied (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFSI]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4])) lie between 0.58 and 0.60, indicating good solvent behavior. The coil dimensions of d-PEO increase on increasing the alkyl chain length of the cation and on decreasing the anion basicity. A more pronounced effect on coil dimensions is observed upon altering the anion, compared to the dependence on cation alkyl chain length. The temperature dependence of $R_{g,0}$ is found to be moderate in 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), where the coil size decreases upon increasing the temperature from 80 to 135 °C. Addition of up to 10 wt % of a salt, lithium bis(trifluoromethylsulfonyl)imide, to mixtures of d-PEO and [BMIM][TFSI] has no significant effect on $R_{g,0}$. These results are discussed in terms of the relative interactions among PEO, the cation, and the anion.},
doi = {10.1021/acs.macromol.9b00354},
journal = {Macromolecules},
number = 8,
volume = 52,
place = {United States},
year = {Fri Apr 12 00:00:00 EDT 2019},
month = {Fri Apr 12 00:00:00 EDT 2019}
}
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https://doi.org/10.1021/acs.macromol.9b00354
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