Design of Clickable Ionic Liquid Monomers to Enhance Ionic Conductivity for Main-Chain 1,2,3-Triazolium-Based Poly(Ionic Liquid)s

Abstract

A series of clickable α-azide-ω-alkyne ionic liquid (IL) monomers with an ethylene oxide spacer were developed and applied to the synthesis of 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) with high ionic conductivities via one-step thermal azide–alkyne cycloaddition click chemistry. Subsequently, the number of IL moieties in the resultant TPILs was further increased by N -alkylation of the 1,2,3-triazole-based backbones of the TPILs with a quarternizing reagent. This strategy affords the preparation of TPILs having either one or two 1,2,3-triazolium cations with bis(trifluoromethylsulfonyl)imide anions in a monomer unit. Synthesis of the TPILs was confirmed by 1 H and 13 C NMR spectroscopy and gel permeation chromatography. The effects of the length of the ethylene oxide spacer and the number of IL moieties in the IL monomer unit on the physicochemical properties of the TPILs were characterized by differential scanning calorimetry, thermogravimetric analysis, and impedance spectroscopy. The introduction of a longer ethylene oxide spacer or an increase in the number of IL moieties in the monomer unit resulted in TPILs with lower glass-transition temperatures and higher ionic conductivities. The highest ionic conductivity achieved in this study was 2.0 × 10 –5 S cm –1 at 30 °C. These results suggest that the design of the IL monomer provides the resultant polymer with high chain flexibility and a high IL density, and so it is effective for preparing TPILs with high ionic conductivities.

Polymerized and Colloidal Ionic Liquids─Syntheses and Applications

“…This aspect was explored by Lindenmeyer and Miller (Section 2.6.1). 93 Hirai et al 94 developed the clickable monomer 15 in order to form a PIL with high ionic conductivity. The azide and alkyne groups thermally condense to form racemic mixtures of 1,2,3-triazole linking groups when heated to about 120 °C.…”

1,3,4,5‐Tetrasubstituted Poly(1,2,3‐triazolium) Obtained through Metal‐Free AA+BB Polyaddition of a Diazide and an Activated Internal Dialkyne

“…[27] The synthesis of this new class of poly(ionic liquid)s has been further extended to a wide variety of functional monomers (with, e.g., aromatic, aliphatic, or ethylene glycol segments) through either AA+BB or AB+AB CuAAC or TAAC polyadditions followed by the N-alkylation of the resulting poly(1,2,3-triazole)s using different alkylating agents and optional ion exchange metathesis. [28][29][30][31][32][33][34][35][36][37] They find interest in a broad range of applications such as antimicrobial materials, [38] CO 2 capture, [39,40] catalysis, [41] electrochromic devices, [32,42] sensors, [43] dye-sensitized solar cells, [44] supercapacitors, [45] or batteries. [46] We report herein the unprecedented synthesis of a 1,3,4,5tetrasubstituted poly(1,2,3-triazolium) in two steps (Scheme 1A) by combining previously reported synthetic strategies, that is, i) the metal-free AA+BB TAAC step growth polymerization of activated internal dialkynes and diazides (Scheme 1B), [23][24][25] and ii) the N-alkylation of 1,3,4-trisubstituted poly(1,2,3-triazole)s obtained by AA+BB CuAAC polyaddition (Scheme 1C).…”

“…[ 27 ] The synthesis of this new class of poly(ionic liquid)s has been further extended to a wide variety of functional monomers (with, e.g., aromatic, aliphatic, or ethylene glycol segments) through either AA+BB or AB+AB CuAAC or TAAC polyadditions followed by the N ‐alkylation of the resulting poly(1,2,3‐triazole)s using different alkylating agents and optional ion exchange metathesis. [ 28–37 ] They find interest in a broad range of applications such as antimicrobial materials, [ 38 ] CO 2 capture, [ 39,40 ] catalysis, [ 41 ] electrochromic devices, [ 32,42 ] sensors, [ 43 ] dye‐sensitized solar cells, [ 44 ] supercapacitors, [ 45 ] or batteries. [ 46 ]…”

Energetic Materials Based on N-substituted 4(5)-nitro-1,2,3-triazoles

“…Along with that, inaccessible N3-substitution products in the series of isomeric N-substituted 4-nitro-1,2,3-triazoles are of special interest for the development of high-energy [26,27], ionic [28][29][30], and polymeric materials [31] and metal complexes [32,33]. Due to the low accessibility, N3-substitution products are almost understudied.…”