Copolymers comprising poly(ethylene oxide) and cationic glycidyl triazolyl polymer with tribranched side chains (PEO--GTP·3X) were synthesized from glycidyl azide copolymer (PEO--GAP) and the tricationic alkyne. A synthetic route for the tricationic alkyne was also improved. Bis(trifluoromethanesulfonyl)imide (TFSI) and bis(fluorosulfonyl)imide (FSI) were used as counteranions. Copolymers PEO--GTP·3TFSI and PEO--GTP·3FSI were characterized by NMR, IR, size exclusion chromatography, DSC, TGA, rheological, and impedance measurements. The NMR results suggested that the main chain of the copolymer was more flexible than that of the homopolymer. However, no major changes were detected in the glass transition temperature and ionic conductivity of the homopolymer and copolymer with TFSI counteranions. The counterion exchange from TFSI to FSI resulted in an increase in the storage modulus and complex viscosity because of the ionic association. Despite its unfavorable viscoelastic properties, PEO--GTP·3FSI exhibited higher ionic conductivity than PEO--GTP·3TFSI (3.9 × 10 S cm at 25 °C under anhydrous conditions).
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