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

A novel imidazolium-containing monomer, 1-[-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 degrees C to -42 degrees C and 2.09 x 10(-7) S cm(-1) to 2.45 x 10(-5) S cm(-1). In particular, PILs with Tf2N counter-ions showed excellent ion conductivity of 2.45 x 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, 1BDIMATf(2)N would not polymerize in acetonitrile (MeCN) at 65 degrees C and only achieved low monomer conversion (< 5%) at 75 degrees C. However, 1BDIMA-Tf2N proceeded to high conversion in dimethylformamide (DMF) at 65 degrees 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. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1346-1357