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Title: Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics

Abstract

A novel imidazolium–containing monomer, 1–[ω–methacryloyloxydecyl]–3–(n–butyl)–imidazolium (1BDIMA), was synthesized and polymerized using free radical and controlled free radical polymerization followed by post–polymerization ion exchange with bromide (Br), tetrafluoroborate (BF4), hexafluorophosphate (PF6), or bis(trifluoromethylsulfonyl)imide (Tf2N). The thermal properties and ionic conductivity of the polymers showed a strong dependence on the counter–ions and had glass transition temperatures (Tg) and ion conductivities at room temperature ranging from 10 °C to –42 °C and 2.09 × 10–7 S cm–1 to 2.45 × 10–5 S cm–1. In particular, PILs with Tf2N counter–ions showed excellent ion conductivity of 2.45 × 10–5 S cm–1 at room temperature without additional ionic liquids (ILs) being added to the system, making them suitable for further study as electro–responsive materials. In addition to the counter–ions, solvent was found to have a significant effect on the reversible addition–fragmentation chain–transfer polymerization (RAFT) for 1BDIMA with different counter–ions. For example, 1BDIMATf2N would not polymerize in acetonitrile (MeCN) at 65 °C and only achieved low monomer conversion (< 5%) at 75 °C. However, 1BDIMA–Tf2N proceeded to high conversion in dimethylformamide (DMF) at 65 °C and 1BDIMABr polymerized significantly faster in DMF compared to MeCN. NMR diffusometry was used to investigate the kinetic differences by probing themore » diffusion coefficients for each monomer and counter–ion in MeCN and DMF. Furthermore, these results indicate that the reaction rates are not diffusion limited, and point to a need for deeper understanding of the role electrostatics plays in the kinetics of free radical polymerizations.« less

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [1];  [1]; ORCiD logo [2]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468237
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part A, Polymer Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 13; Journal ID: ISSN 0887-624X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; counter‐ion effect; ion conductivity; ion‐containing polymers; poly(ionic liquid)s; reversible addition-fragmentation chain transfer polymerization (RAFT)

Citation Formats

Chen, Mingtao, Dugger, Jason W., Li, Xiuli, Wang, Yangyang, Kumar, Rajeev, Meek, Kelly M., Uhrig, David W., Browning, James F., Madsen, Louis A., Long, Timothy E., and Lokitz, Bradley S. Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics. United States: N. p., 2018. Web. doi:10.1002/pola.29015.
Chen, Mingtao, Dugger, Jason W., Li, Xiuli, Wang, Yangyang, Kumar, Rajeev, Meek, Kelly M., Uhrig, David W., Browning, James F., Madsen, Louis A., Long, Timothy E., & Lokitz, Bradley S. Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics. United States. doi:10.1002/pola.29015.
Chen, Mingtao, Dugger, Jason W., Li, Xiuli, Wang, Yangyang, Kumar, Rajeev, Meek, Kelly M., Uhrig, David W., Browning, James F., Madsen, Louis A., Long, Timothy E., and Lokitz, Bradley S. Mon . "Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics". United States. doi:10.1002/pola.29015. https://www.osti.gov/servlets/purl/1468237.
@article{osti_1468237,
title = {Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics},
author = {Chen, Mingtao and Dugger, Jason W. and Li, Xiuli and Wang, Yangyang and Kumar, Rajeev and Meek, Kelly M. and Uhrig, David W. and Browning, James F. and Madsen, Louis A. and Long, Timothy E. and Lokitz, Bradley S.},
abstractNote = {A novel imidazolium–containing monomer, 1–[ω–methacryloyloxydecyl]–3–(n–butyl)–imidazolium (1BDIMA), was synthesized and polymerized using free radical and controlled free radical polymerization followed by post–polymerization ion exchange with bromide (Br), tetrafluoroborate (BF4), hexafluorophosphate (PF6), or bis(trifluoromethylsulfonyl)imide (Tf2N). The thermal properties and ionic conductivity of the polymers showed a strong dependence on the counter–ions and had glass transition temperatures (Tg) and ion conductivities at room temperature ranging from 10 °C to –42 °C and 2.09 × 10–7 S cm–1 to 2.45 × 10–5 S cm–1. In particular, PILs with Tf2N counter–ions showed excellent ion conductivity of 2.45 × 10–5 S cm–1 at room temperature without additional ionic liquids (ILs) being added to the system, making them suitable for further study as electro–responsive materials. In addition to the counter–ions, solvent was found to have a significant effect on the reversible addition–fragmentation chain–transfer polymerization (RAFT) for 1BDIMA with different counter–ions. For example, 1BDIMATf2N would not polymerize in acetonitrile (MeCN) at 65 °C and only achieved low monomer conversion (< 5%) at 75 °C. However, 1BDIMA–Tf2N proceeded to high conversion in dimethylformamide (DMF) at 65 °C and 1BDIMABr polymerized significantly faster in DMF compared to MeCN. NMR diffusometry was used to investigate the kinetic differences by probing the diffusion coefficients for each monomer and counter–ion in MeCN and DMF. Furthermore, these results indicate that the reaction rates are not diffusion limited, and point to a need for deeper understanding of the role electrostatics plays in the kinetics of free radical polymerizations.},
doi = {10.1002/pola.29015},
journal = {Journal of Polymer Science. Part A, Polymer Chemistry},
number = 13,
volume = 56,
place = {United States},
year = {2018},
month = {4}
}

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