In this work, two fluorinated poly(1,2,3-triazolium ionic liquid)s (PTILs) are accessed in two steps by copper(I)-catalyzed azide-alkyne cycloaddition AA + BB polyaddition between an α,ω-dialkyne-perfluoroether and either 1,12-dodecyl-diazide or α,ω-diazido-tetra(ethylene glycol), followed by N-alkylation of the resulting poly(1,2,3-triazole)s (PTs) by N-methyl bis(trifluoromethylsulfonyl)imide. The structure/properties correlations of PTILs and their PT intermediates are discussed based on solubility, 1 H, 13 C and 19 F NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and broadband dielectric spectroscopy. Dodecyl-and tetra(ethylene glycol)-based PTILs exhibit glass transition temperatures of − 38 and − 29 °C, temperatures at 10% weight loss of ca. 340 °C and anhydrous ionic conductivities at 30 °C of 1.2 × 10 −5 and 8.4 × 10 −6 S cm −1 , respectively. The impact of different lithium salts (i.e. LiSO 3 CF 3 , LiTFSI, and LiClO 4 ,) on ionic conductivity of the tetra(ethylene glycol)-based PTIL was also investigated. A ca. twofold increase in ionic conductivity could be obtained by the addition of 5 wt% of LiClO 4 .

Partially biobased poly­(1,2,3-triazolium)­s are synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization of tailor-made 1,2,3-triazole-functionalized (meth)­acrylate monomers derived from levulinic acid, followed by N-alkylation of the 1,2,3-triazole moieties by methyl iodide (CH3I) and subsequent anion exchange with lithium bis­(trifluoromethylsulfonyl)­imide (LiTFSI). Chain extension of a 1,2,3-triazole-functionalized polymethacrylate by RAFT polymerization of styrene followed by N-alkylation with CH3I and anion exchange with LiTFSI affords two poly­(1,2,3-triazole)- and two poly­(1,2,3-triazolium)-based diblock copolymers (BCPs) with different weight fractions of each block. Discussion of the structure/properties relationships of all obtained materials is based on NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, thermogravimetric analysis, and broadband dielectric spectroscopy. The morphological and self-assembling properties of neutral and charged BCPs in bulk and in thin films are investigated by small-angle X-ray scattering and atomic force microscopy experiments, respectively.