Triethylene glycol-based poly(1,2,3-triazolium acrylate)s with enhanced ionic conductivity

Abstract

International audienceA series of cationic poly(acrylate ionic liquid)s having a triethylene glycol (TEG) spacer and a pendant 1,2,3-triazolium group is synthesized by post-polymerization sequential chemical modifications. A chloride-functionalized polyacrylate common precursor is first obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization of a TEG-based chloride-functionalized acrylate. Sequential azidation, copper-catalyzed azide-alkyne cycloaddition with 1-pentyne and alkylation of the resulting 1,2,3-triazole by methyl iodide affords a poly(acrylate ionic liquid) having pendant 3-methyl-4-propyl-1,2,3-triazolium iodide groups. Further anion metathesis with three different fluorinated salts yields a series of 1,2,3-triazolium-based PILs with distinct counter anions. The polymer precursors and resulting poly(1,2,3-triazolium ionic liquid) s (PTILs) are characterized by H-1 NMR spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and broadband dielectric spectroscopy (BDS). Well-defined PTIL derivative with bis(trifluoromethane) sulfonimide anion (M-n = 113,600 g mol(-1) and D = 1.23) exhibits the lowest glass transition temperature (T-g = -36 degrees C), the highest thermal stability (T-d10 = 321 degrees C) and the highest anhydrous ionic conductivity (sigma(DC) = 1.1 x 10(-5) S cm(-1) at 30 degrees C) of the series

Imidazolium‐based poly(ionic liquid)s with poly(ethylene oxide) main chains: Effects of spacer and tail structures on ionic conductivity

“…They confirmed that poly(ionic liquid)s with molecular weights less than 500 kDa showed a strong molecular weight dependency of their ionic conductivity . In conventional studies, most of poly(ionic liquid)s are prepared from ionic liquid monomers by radical polymerization . In such cases, the change in the ionic conductivity is attributable not only to the change in the chemical structure but also to the difference in the molecular weight.…”

“…To date, various types of poly(ionic liquid)s have been reported . Their reported ionic conductivity values range from 10 −8 to 10 −4 S cm −1 at room temperature.…”

Poly(1,2,3-triazolium)s: a new class of functional polymer electrolytes

“…The use of a common neutral polymer precursor with well-defined structural characteristics for the development of a series of PILs with different counter-anions permits to exclusively pinpoint the impact of the counteranion and to establish a precise structure-property relationship.Polyacrylate-based TPILs 29-32 having a triethylene glycol (TEG) spacer were then prepared using a parallel yet significantly different approach based on post-polymerization azidation and CuAAC reactions(Fig. 7b) 71. RAFT polymerization of chloride-functionalized acrylate 24 using trithiocarbonate 25 as chain transfer agent and V-70 as initiator afforded polyacrylate 26 (M n SEC = 24 kDa, Ð = 1.33, CHCl 3 , PS standards), the common neutral precursor of PT 28 and TPILs 29-32.…”

Quaternary Ammonium Cation Functionalized Poly(Ionic Liquid)s with Poly(Ethylene Oxide) Main Chains

“…Figure a shows the relationship between the σ DC value and reciprocal temperature for the cationic GTPs with the N ‐methyl substituent. The ionic conductivities of all cationic GTPs followed Vogel–Fulcher–Tammann (VFT) type temperature dependence, which reflects the coupling of the segmental motion of the polymer and the ion transport . The data were fitted with the following equationwhere σ ∞ is the ionic conductivity at T → ∞, D σ is the strength parameter related to the divergence from the Arrhenius temperature dependence, and T σ is the Vogel temperature at which the free volume extrapolates to zero.…”