Glycidyl triazolyl polymer (GTP)-based anionic poly(ionic
liquid)s
comprising the trifluoromethanesulfonimide (TFSI) anion pendant and
the 1-ethyl-3-methylimidazolium (EMIM) countercation were synthesized
through Cu(I)-catalyzed azide–alkyne cycloaddition between
a glycidyl azide polymer and anionic alkyne derivatives. These polymers
were designed as oppositely charged analogs of the cationic GTPs reported
previously. The anionic GTPs were characterized by NMR, IR, size-exclusion
chromatography, differential scanning calorimetry, thermogravimetric
analysis, and impedance measurements. The anionic GTPs reported herein
exhibited a lower critical solution temperature (LCST) type phase
separation in acetone. The anionic GTPs with a longer side-chain spacer
exhibited a lower glass transition temperature (T
g) and higher ionic conductivity (1.7 × 10–6 S cm–1 at 25 °C under anhydrous conditions).
It was confirmed that the anionic GTPs contain 0.8–0.9 wt %
water even after the drying process. It is considered that the residual
water contributes to improving the ionic conductivity. Compared to
the cationic GTP with a similar side-chain spacer, the anionic GTP
exhibited higher T
g and lower ionic conductivity.
The analysis based on the electrode polarization model indicated that
the lower ionic conductivity would originate from lower conducting
ion concentration and mobility. From the conducting ion mobility versus T
g/T plot, it was confirmed
that the anionic GTP with the short alkyl chain spacer gave higher
conducting ion mobility than that with the ethylene oxide spacer,
which suggested that the electrostatic interaction with the ether
oxygen atoms could slow down the diffusion of the EMIM cation. Stronger
electrostatic interaction between the TFSI pendant and EMIM cation
than that between the EMIM pendant and TFSI counterion is a cause
of stronger polymer–polymer interaction.