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 E.; Lokitz, Bradley S.

doi:10.1002/pola.29015

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

Journal Article · 16 April 2018 · Journal of Polymer Science. Part A, Polymer Chemistry

DOI: https://doi.org/10.1002/pola.29015 · OSTI ID:1468237

Chen, Mingtao ^[1];

^[2]; Li, Xiuli ^[1];

^[2];

^[2]; Madsen, Louis A. ^[1]; Long, Timothy E. ^[1];

^[2]

Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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. 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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1468237

Journal Information:: Journal of Polymer Science. Part A, Polymer Chemistry, Vol. 56, Issue 13; ISSN 0887-624X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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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)

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

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