Mass and charge transport in 1-alkyl-3-methylimidazolium triflate ionic liquids.
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ABSTRACT:
SUBMITTER: Petrowsky M
PROVIDER: S-EPMC3862598 | biostudies-other | 2013 Nov
REPOSITORIES: biostudies-other
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Project description:The functionalization of polymers with sulfonate groups has many important uses, ranging from biomedical applications to detergency properties used in oil-recovery processes. In this work, several ionic liquids (ILs) combining 1-alkyl-3-methylimidazolium cations [CnC1im]+ (4 ≤ n ≤ 8) with alkyl-sulfonate anions [CmSO3]- (4 ≤ m ≤ 8) have been studied using molecular dynamics simulations, totalizing nine ionic liquids belonging to two homologous series. The radial distribution functions, structure factors, aggregation analyses, and spatial distribution functions reveal that the increase in aliphatic chain length induces no significant change in the structure of the polar network of the ILs. However, for imidazolium cations and sulfonate anions with shorter alkyl chains, the nonpolar organization is conditioned by the forces acting on the polar domains, namely, electrostatic interactions and hydrogen bonding.
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Project description:Tunable aryl alkyl ionic liquids (TAAILs) based on the imidazolium cation were first reported in 2009. Since then, a series of TAAILs with different properties due to the electron-donating or -withdrawing effect of the substituents at the aryl ring has been developed. Herein, a wide variety of those ionic liquids (ILs) is presented in terms of their cation structure. The authors synthesized ILs containing the bromide or bis(trifluoromethane)sulfonimide anion and 1-aryl-3-alkyl imidazolium cations with various substituents in the ortho and/ or para position of the phenyl ring and alkyl chains of different lengths varying from butyl to dodecyl. The differences of their physical properties (melting point, thermal decomposition, viscosity, electro-chemical window) of these ILs are reported according to their structure.
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Project description:Molecular ionic liquids are typically characterized by strong electrostatic interactions resulting in a charge ordering and retardation of their translational and rotational behaviour. Unfortunately, this effect is often overestimated in classical molecular dynamics simulations. This can be circumvented in a twofold way: the easiest way is to reduce the partial charges of the ions to sub-integer values of ±0.7-0.9 e. The more realistic model is to include polarizable forces, e.g. Drude-oscillators, but it comes along with an increasing computational effort. On the other hand, charge-scaled models are claimed to take an average polarizability into account. But do both models have the same impact on structure and dynamics of molecular ionic liquids? In the present study several molecular dynamics simulations of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate are performed with different levels of polarization as well as with varying charge scaling factors of 0.74 to 0.90. The analysis of the structural and dynamical results are performed in different levels: from the atomic point of view over the molecular level to collective properties determined by the complete sample.
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Project description:Herein, a solvent-based green recycling procedure is reported for recycling thermoset epoxy resins (TERs) and carbon fiber reinforced epoxy composites (CFRECs) employing ionic liquids (ILs) and alcohols under mild conditions. With melting points less than 100 °C, ILs are defined as organic salts, typically composed of bulky cations with organic or inorganic counteranions. As a result of their unique physical properties such as low vapor pressure, relatively high thermal stability, and multifunctional tunability, these solvents are often classified as "green solvents" as compared to traditional organic solvents. In this study, swelling and dissolution of TER are evaluated in the presence of pure alkyl-methyl-imidazolium ILs, alcohols, and various mixtures of these co-solvents to determine their swelling and depolymerization capacity at mild temperatures in the absence of catalysts. In these studies, three ILs with different alkyl lengths were evaluated: 1-butyl-3-methyl imidazolium chloride ([BMIm][Cl]), 1-hexyl-3-methyl imidazolium bromide ([HMIm][Br]), and 1-octyl-3-methyl imidazolium bromide ([OMIm][Br]) along with two alcohols: ethylene glycol (EG) and glycerol (Gly). The highest swelling capacity of TER at 150 °C was achieved by a combination of [BMIm][Cl] and EG. In addition, swelling and dissolution of TER were evaluated in the presence of several anion variants of 1-butyl-3-methyl-imidazolium ILs with EG. Complete dissolution of both TERs and CFRECs was achieved in 150 min (2.5 h) at 150 °C under atmospheric pressure. Finally, recovery and reuse of the recycled monomer after dissolution were examined. Recovered epoxy monomers employed to synthesize a recycled TER exhibited similar mechanical properties to the parent TER. In addition, it was demonstrated that carbon fibers could be successfully recovered from CFREC using the recycling method detailed in this manuscript.
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