We present first results on triazolium-based ionic liquids (ILs) as a novel class of nonderivatizing solvents for cellulose. Despite their chemical similarity to imidazolium cations, the 1,2,3-triazolium cation lacks the isolated ring proton, leading to reduced formation of N-heterocyclic carbenes (NHCs) and therefore to lower reactivity and less unwanted side reactions. We synthesized six ILs based on 1,2,3-triazolium and 1,2,4-triazolium cations. The acetates are room-temperature ionic liquids and dissolve a similar amount of cellulose as the corresponding imidazolium salt. From NMR spectroscopy of the solution, we rule out polymer degradation. The cellulose solubility rises with increasing anion basicity, while being almost independent of the cation. We perform molecular dynamics simulations and compute enthalpies of solvation, which quantitatively fit the experimental solubilities. Trajectory analysis reveals strong hydrogen bonds between acetate anions and cellulose hydroxyl groups, while the cations do not form strong hydrogen bonds with cellulose. Thus, the simulations provide an atomistic explanation of our experimental observations.
Poly(ethylene oxide) (PEO) is a polymer of great interest due to its prevalence in biomedical, pharmaceutical, and ion conductive systems. In this study, the crystallization behaviors of a PEO with 22 monomer units (PEO22) and a PEO having the same degree of polymerization but with an additional 1,4-disubstituted 1,2,3-triazole ring in central position of the chain (PEO11-TR-PEO11) are investigated. PEO11-TR-PEO11 shows one type of lamella crystal after cooling to T = 0 °C, but structural changes during heating below their final melting are detected by WAXS, DSC, POM, and solid-state NMR spectroscopy. The lamella thickness increases, but simultaneously the helix–helix distance decreases and an additional Bragg reflection appears at 2θ = 22.1°. A model is proposed which explains these structural changes by incorporation of the TR ring into the crystals which are additionally stabilized by attractive C–H···π interactions of the TR rings. Additionally, two different types of extended chain lamella crystals are found in PEO22 by SAXS which are discussed in the context of fractionation caused by the molar mass distribution obtained from MALDI-ToF data.
1,2,3-Triazole (TR) is a good proton conductor which is tidely related to formation of a hydrogen bond network along the N-HN trajectory and its self-dissociation into diH-1,2,3-triazolium and 1,2,3-triazolate. To gain a deeper understanding, the proton conductivity of TR is measured by impedance spectroscopy (IS) across its melting temperature and an additionally discovered solid-solid phase transition. The orthorhombic high temperature phase and the monoclinic low temperature modification are investigated by polarized optical microscopy, DSC- and WAXS measurements. Furthermore, the diffusion coefficients of TR are determined from IS data and measured by (1)H PFG NMR spectroscopy in the melt which allows for separate evaluation of contributions of proton hopping across the hydrogen bond network and the vehicle mechanism to the proton conductivity where the vehicles are defined as charged species generated by TR self-dissociation. Finally, the degree of dissociation of TR is calculated and the influence of the self-dissociation of TR on the proton conductivity is discussed in the context of the dielectric constant.
We present 1,2,3-triazolium- and imidazolium-based ionic liquids (ILs) with aromatic anions as a new class of cellulose solvents. The two anions in our study, benzoate and salicylate, possess a lower basicity when compared to acetate and therefore should lead to a lower amount of N-heterocyclic carbenes (NHCs) in the ILs. We characterize their physicochemical properties and find that all of them are liquids at room temperature. By applying force field molecular dynamics (MD) simulations, we investigate the structure and dynamics of the liquids and find strong and long-lived hydrogen bonds, as well as significant π–π stacking between the aromatic anion and cation. Our ILs dissolve up to 8.5 wt.-% cellulose. Via NMR spectroscopy of the solution, we rule out chain degradation or derivatization, even after several weeks at elevated temperature. Based on our MD simulations, we estimate the enthalpy of solvation and derive a simple model for semi-quantitative prediction of cellulose solubility in ILs. With the help of Sankey diagrams, we illustrate the hydrogen bond network topology of the solutions, which is characterized by competing hydrogen bond donors and acceptors. The hydrogen bonds between cellulose and the anions possess average lifetimes in the nanosecond range, which is longer than found in common pure ILs.
Polymer electrolytes are of tremendous importance for applications in modern lithium-ion (Li + -ion) batteries due to their satisfactory ion conductivity, low toxicity, reduced flammability, as well as good mechanical and thermal stability. In this study, the Li + -ion conductivity of well-defined poly(ethylene oxide) (PEO) networks synthesized via copper(I)-catalyzed azidealkyne cycloaddition is investigated by electrochemical impedance spectroscopy after addition of different lithium salts. The ion conductivity of the network electrolytes increases with increasing molar mass of the PEO chains between the junction points which is completely opposite to the behavior of their respective uncrosslinked linear precursors. Obviously, this effect is directly related to the segmental mobility of the PEO chains. Furthermore, the ion conductivity of the network electrolytes under investigation increases also with increasing size of the anion of the added lithium salt due to a weaker anti-plasticizing effect of the more bulky anions.
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