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 E. Long; Bradley S. Lokitz

doi:10.1002/pola.29015

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 E. Long, Bradley S. Lokitz

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

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 (T_g) 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 language	English
Pages (from-to)	1346-1357
Number of pages	12
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	56
Issue number	13
DOIs	https://doi.org/10.1002/pola.29015
State	Published - Jul 1 2018

Funding

This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/ downloads/doe-public-access-plan).

Funders	Funder number
U. S. Department of Energy
US National Science Foundation	DMR 1507764
National Science Foundation	1507764
Oak Ridge National Laboratory

Keywords

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

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@article{fc963988a30340c4aeee3762a192b1fa,

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 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.",

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

author = "Mingtao Chen and Dugger, {Jason W.} and Xiuli Li and Yangyang Wang and Rajeev Kumar and Meek, {Kelly M.} and Uhrig, {David W.} and Browning, {James F.} and Madsen, {Louis A.} and Long, {Timothy E.} and Lokitz, {Bradley S.}",

note = "Publisher Copyright: {\textcopyright} 2018 Wiley Periodicals, Inc.",

year = "2018",

month = jul,

day = "1",

doi = "10.1002/pola.29015",

language = "English",

volume = "56",

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journal = "Journal of Polymer Science, Part A: Polymer Chemistry",

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TY - JOUR

T1 - Polymerized ionic liquids

T2 - Effects of counter-anions on ion conduction and polymerization kinetics

AU - Chen, Mingtao

AU - Dugger, Jason W.

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 E.

AU - Lokitz, Bradley S.

PY - 2018/7/1

Y1 - 2018/7/1

N2 - 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.

AB - 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.

KW - counter-ion effect

KW - ion conductivity

KW - ion-containing polymers

KW - poly(ionic liquid)s

KW - reversible addition-fragmentation chain transfer polymerization (RAFT)

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DO - 10.1002/pola.29015

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JO - Journal of Polymer Science, Part A: Polymer Chemistry

JF - Journal of Polymer Science, Part A: Polymer Chemistry

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ER -

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

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