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

Mingtao Chen, Jason W. Dugger, Xiuli Li, Yangyang Wang, Rajeev Kumar, Kelly M. Meek, David W. Uhrig, James F. Browning, Louis A. Madsen, Timothy Edward Long, Bradley S. Lokitz

Research output: Contribution to journalArticle

5 Citations (Scopus)

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 the diffusion coefficients for each monomer and counter-ion in MeCN and DMF. 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.

Original languageEnglish
Pages (from-to)1346-1357
Number of pages12
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume56
Issue number13
DOIs
Publication statusPublished - 2018 Jul 1
Externally publishedYes

Fingerprint

Ionic Liquids
Radiation counters
Ionic liquids
Anions
Negative ions
Dimethylformamide
Polymerization
Ions
Kinetics
Monomers
Free radical polymerization
Imides
Ionic conductivity
Acetonitrile
Bromides
Free radicals
Reaction rates
Free Radicals
Electrostatics
Ion exchange

Keywords

  • counter-ion effect
  • ion conductivity
  • ion-containing polymers
  • poly(ionic liquid)s
  • reversible addition-fragmentation chain transfer polymerization (RAFT)

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Polymerized ionic liquids : Effects of counter-anions on ion conduction and polymerization kinetics. / 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 Edward; Lokitz, Bradley S.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 56, No. 13, 01.07.2018, p. 1346-1357.

Research output: Contribution to journalArticle

Chen, M, Dugger, JW, Li, X, Wang, Y, Kumar, R, Meek, KM, Uhrig, DW, Browning, JF, Madsen, LA, Long, TE & Lokitz, BS 2018, 'Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics', Journal of Polymer Science, Part A: Polymer Chemistry, vol. 56, no. 13, pp. 1346-1357. https://doi.org/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 Edward ; Lokitz, Bradley S. / Polymerized ionic liquids : Effects of counter-anions on ion conduction and polymerization kinetics. In: Journal of Polymer Science, Part A: Polymer Chemistry. 2018 ; Vol. 56, No. 13. pp. 1346-1357.
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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 the diffusion coefficients for each monomer and counter-ion in MeCN and DMF. 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.",
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AU - Li, Xiuli

AU - Wang, Yangyang

AU - Kumar, Rajeev

AU - Meek, Kelly M.

AU - Uhrig, David W.

AU - Browning, James F.

AU - Madsen, Louis A.

AU - Long, Timothy Edward

AU - Lokitz, Bradley S.

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