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Properties and Applications of Ionic Liquids

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (31 December 2020) | Viewed by 28691

Special Issue Editor


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Guest Editor
Institute of Polymer and Dye Technology, Lodz University of Technology, Lodz, Poland
Interests: elastomer composites; application of ionic liquids in polymers; vulcanization of elastomers; crosslinking agents and fillers for polymers; thermal analysis of polymeric materials and additives for polymer composites; elimination of allergenic compounds from rubber products
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Special Issue Information

Dear Colleagues,

In recent years, scientists and engineers have become increasingly interested in ionic liquids (ILs) because of their structures, and, consequently, their properties can be easily tailored for specific applications. Therefore, ILs are considered “designer solvents”. Owing to negligible vapor pressure, non-flammability, thermal stability, and catalytic activity, ILs have become an environmentally friendly alternative to the volatile organic solvents in organic synthesis, various types of polymerizations, extraction processes, catalysis and biocatalysis, electrochemistry, and biomass processing. Furthermore, ILs have attracted much attention for applications in polymeric and elastomeric composites, mainly as dispersing agents and modifiers of fillers, catalysts for the silanization of silica, conductive additives, vulcanization activators and accelerators, curing agents for resins, and plasticizers for thermoplastics. As was mentioned, the variety of cations and anions allows the structure of ILs to be properly designed to show specific properties and thus to find specific applications. Recently, new classes of task-specific ILs, color-shifting Ils, and antiherbicidal ILs have been developed and studied. It can be expected that the use of ILs in different fields of science and technology will continue to increase in the near future.

This Special Issue concerns all aspects related to recent progress in the synthesis of multifunctional ILs, their characterization with regards to physicochemical properties; thermal behavior, and biological and catalytic activity; as well as broadly understood applications of ILs, among others, in organic and inorganic synthesis, separation techniques and extraction processes, catalysis, electrochemistry, and polymer and elastomer composites.

I kindly invite all researches interested in ionic liquid synthesis, properties, and wide applications, to submit a manuscript(s) for this Special Issue. Full papers, communications, and reviews are all welcome.

Dr. Magdalena Maciejewska
Guest Editor

Manuscript Submission Information

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Keywords

  • ILs synthesis
  • Task-specific and multifunctional ILs
  • Polymerized ILs
  • Physical and electrochemical properties
  • Thermal behavior
  • Catalytic and biological activity
  • Green solvents and reaction medium
  • Curatives, vulcanization activators, and accelerators
  • Dispersing agents
  • Conductive additives
  • Biomass processing.

Published Papers (11 papers)

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Research

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13 pages, 3452 KiB  
Article
Solubility of Carbon Dioxide in Deep Eutectic Solvents Based on 3-Amino-1-Propanol and Tetraalkylammonium Salts at Low Pressure
by Iwona Cichowska-Kopczyńska, Dorota Warmińska and Bartosz Nowosielski
Materials 2021, 14(3), 594; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14030594 - 27 Jan 2021
Cited by 11 | Viewed by 2388
Abstract
Deep eutectic solvents (DESs) became an object of a great interest as an alternative to ionic liquids (ILs) and commonly used in CO2 capture amine solutions. In the present study, five different DESs based on 3-amino-1-propanol as physical-chemical CO2 absorbents were [...] Read more.
Deep eutectic solvents (DESs) became an object of a great interest as an alternative to ionic liquids (ILs) and commonly used in CO2 capture amine solutions. In the present study, five different DESs based on 3-amino-1-propanol as physical-chemical CO2 absorbents were used. The composition was chosen in order to estimate the effects of hydrogen bond acceptor:hydrogen bond donor (HBA:HBD) molar ratio, anion type and length of alkyl chain of composing salt. The Fourier Transform Infrared (FTIR) spectroscopy was used to confirm chemical reaction. The solubility of CO2 was measured at low pressures up to 170 kPa at the temperature range of 293–318 K. Viscosity, polarity and Kamlet–Taft parameters were determined in order to estimate the dependences of the parameters and the CO2 capacity. CO2 uptake was observed to improve with decreasing molar ratio of hydrogen bond donor. Comparing the CO2 capacity of [TBAC]-based DESs, at the approximate pressure of 50 kPa, it was observed that the capacity increased in the following order of molar ratios—1:8 < 1:6 < 1:4 and a decrease in molar ratio from 1:8 to 1:4 resulted in about a 100% increase of capacity. Compared to [TBAC][AP] DESs, the [TEAC][AP] 1:4 and [TBAB][AP] 1:4 exhibited higher CO2 uptake, though the best results were obtained for [TBAB][AP]. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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17 pages, 20071 KiB  
Article
Preparation and Properties of SBR Composites Containing Graphene Nanoplatelets Modified with Pyridinium Derivative
by Magdalena Gaca, Cyril Vaulot, Magdalena Maciejewska and Magdalena Lipińska
Materials 2020, 13(23), 5407; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13235407 - 27 Nov 2020
Cited by 9 | Viewed by 1781
Abstract
The goal of this work was to study the effect of graphene nanoplatelets (GnPs) modified with ionic liquid (IL) on properties of styrene–butadiene rubber (SBR) composites. GnPs were decorated with IL or were modified in bulk directly during rubber mix preparation. The ionic [...] Read more.
The goal of this work was to study the effect of graphene nanoplatelets (GnPs) modified with ionic liquid (IL) on properties of styrene–butadiene rubber (SBR) composites. GnPs were decorated with IL or were modified in bulk directly during rubber mix preparation. The ionic liquid used was 1-butyl-4-methylpyridinium tetrafluoroborate (BMPFB). The textural properties were studied to confirm surface modification of GnPs with BMPFB. In these investigations, the impact of the concentration of GnPs and the effect of the method of GnPs’ modification with IL on elastomers properties are described. Some thermal measurements (e.g., differential scanning calorimetry and thermogravimetry) were conducted to characterize the thermal stability or the vulcanization process of the investigated samples. Complementary experimental techniques were used to investigate the properties of the obtained elastomers, specifically tensile testing, and electrical and barrier property measurements. The deposition of IL on the GnPs’ surface positively influenced the mechanical and barrier properties of elastomers. However, samples containing graphene nanoplatelets modified from solution were characterized by less electrical conductivity. SEM analysis was additionally performed to investigate GnPs’ dispersion within SBR composites. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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24 pages, 8707 KiB  
Article
UV-Cured Poly(Siloxane-Urethane)-Based Polymer Composite Materials for Lithium Ion Batteries—The Effect of Modification with Ionic Liquids
by Janusz Kozakiewicz, Jarosław Przybylski, Bartosz Hamankiewicz, Krystyna Sylwestrzak, Joanna Trzaskowska, Michal Krajewski, Maciej Ratyński, Witold Sarna and Andrzej Czerwiński
Materials 2020, 13(21), 4978; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13214978 - 5 Nov 2020
Cited by 10 | Viewed by 2951
Abstract
The results of studies on the synthesis and characterization of conductive polymer composite materials designed as potential separators for lithium ion batteries are presented. The conductive polymer composites were prepared from UV-cured poly(siloxane-urethanes)s (PSURs) containing poly(ethylene oxide) (PEO) segments and modified with lithium [...] Read more.
The results of studies on the synthesis and characterization of conductive polymer composite materials designed as potential separators for lithium ion batteries are presented. The conductive polymer composites were prepared from UV-cured poly(siloxane-urethanes)s (PSURs) containing poly(ethylene oxide) (PEO) segments and modified with lithium salts and ionic liquids (ILs). The most encouraging results in terms of specific conductivity and mechanical properties of the composite were obtained when part of UV-curable PSUR prepolymer was replaced with a reactive UV-curable IL. Morphology of the composites modified with ILs or containing a standard ethylene carbonate/dimethyl carbonate mixture (EC/DMC) as solvent was compared. It was found that the composites showed a two-phase structure that did not change when non-reactive ILs were applied instead of EC/DMC but was much affected when reactive UV-curable ILs were used. The selected IL-modified UV-cured PSUR composite that did not contain flammable EC/DMC solvent was preliminarily tested as gel polymer electrolyte and separator for lithium ion batteries. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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16 pages, 4552 KiB  
Article
Dynamics of Ionic Liquids in Confinement by Means of NMR Relaxometry—EMIM-FSI in a Silica Matrix as an Example
by Danuta Kruk, Milosz Wojciechowski, Malgorzata Florek-Wojciechowska and Rajendra Kumar Singh
Materials 2020, 13(19), 4351; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13194351 - 30 Sep 2020
Cited by 16 | Viewed by 2065
Abstract
1H and 19F spin–lattice relaxation studies for 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide in bulk and mesoporous MCM-41 silica matrix confinement were performed under varying temperatures in a broad range of magnetic fields, corresponding to 1H resonance frequency from 5Hz to 30MHz.A thorough analysis [...] Read more.
1H and 19F spin–lattice relaxation studies for 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide in bulk and mesoporous MCM-41 silica matrix confinement were performed under varying temperatures in a broad range of magnetic fields, corresponding to 1H resonance frequency from 5Hz to 30MHz.A thorough analysis of the relaxation data revealed a three-dimensional translation diffusion of the ions in the bulk liquid and two-dimensional diffusion in the vicinity of the confining walls in the confinement. Parameters describing the translation dynamics were determined and compared. The rotational motion of both kinds of ions in the confinement was described by two correlation times that might be attributed to anisotropic reorientation of these species. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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14 pages, 3456 KiB  
Article
The Essential Role of 1-Butyl-3-Methylimidazolium-Based Ionic Liquids in the Development of Transparent Silica-Filled Elastomer Systems
by Małgorzata Kuśmierek, Bolesław Szadkowski and Anna Marzec
Materials 2020, 13(19), 4337; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13194337 - 29 Sep 2020
Cited by 2 | Viewed by 1647
Abstract
In this paper, we present the design of reinforced silica-filled elastomer composites exhibiting a high transparency, high mechanical performance in static and dynamic conditions, and improved electrical conductivity. Two different imidazolium ionic liquids (ILs) were used with increasing loads: 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIMTFSI) and [...] Read more.
In this paper, we present the design of reinforced silica-filled elastomer composites exhibiting a high transparency, high mechanical performance in static and dynamic conditions, and improved electrical conductivity. Two different imidazolium ionic liquids (ILs) were used with increasing loads: 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIMTFSI) and 1-butyl-3-methylimidazolium tetrachloroaluminate (BMIMAlCl4). The composites were prepared in a two-roll mill. The influence of the ILs on the dispersion of the silica in the nitrile rubber (NBR) matrix was assessed by scanning electron microscopy (SEM). The presence of ILs in the NBR/SiO2 systems improved the crosslink density and ionic conductivity of the composites. Their mechanical properties and aging stability remained almost unchanged, at a very satisfactory level. Greater crosslinking was observed for the NBR/SiO2 composites containing BMIMAlCl4, due to its catalytic effect on the efficiency of interface crosslinking reactions. We found the optimal formulation for obtaining transparent reinforced NBR/SiO2 composites. The application of 2.5 phr of BMIMAlCl4 resulted in a high transparency in the case of NBR composites filled with 30 phr of silica. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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21 pages, 6392 KiB  
Article
Ionic Liquids and Calcium Oxide Grafted with Allylmalonic Acid Applied to Support the Peroxide Crosslinking of an Ethylene–Propylene Copolymer
by Magdalena Maciejewska
Materials 2020, 13(15), 3260; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13153260 - 22 Jul 2020
Cited by 1 | Viewed by 2110
Abstract
Nanosized calcium oxide (CaO) featuring a surface grafted with allylmalonic acid (ALA) was used to increase the efficiency of the peroxide crosslinking of an ethylene–propylene copolymer (EPM) filled with silica nanoparticles. In this study, 1-butyl-3-methylimidazolium ionic liquids (ILs) with different anions were applied [...] Read more.
Nanosized calcium oxide (CaO) featuring a surface grafted with allylmalonic acid (ALA) was used to increase the efficiency of the peroxide crosslinking of an ethylene–propylene copolymer (EPM) filled with silica nanoparticles. In this study, 1-butyl-3-methylimidazolium ionic liquids (ILs) with different anions were applied to improve the dispersion of CaO/ALA and silica nanoparticles in the EPM copolymer, as well as to catalyze the interfacial crosslinking reactions. In this article, we discuss the effects of CaO/ALA and ILs on the curing characteristics, vulcanization temperature, crosslink density, mechanical properties, and thermal stability of EPM, as well as the resistance of EPM to weather aging. The CaO/ALA with ILs reduced the vulcanization time of the rubber compounds without a significant effect on the vulcanization temperature. Their application resulted in an increased vulcanizate crosslink density, as well as improved tensile strength compared to the pure peroxide system. The influence of 1-butyl-3-methylimidazolium ILs on EPM vulcanization and performance depends on the anion present in the molecules of the ionic liquid. The most active IL seems to be that with the tetrafluoroborate anion. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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11 pages, 1113 KiB  
Article
Representation of the Structure—A Key Point of Building QSAR/QSPR Models for Ionic Liquids
by Anna Rybińska-Fryca, Anita Sosnowska and Tomasz Puzyn
Materials 2020, 13(11), 2500; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13112500 - 30 May 2020
Cited by 9 | Viewed by 3183
Abstract
The process of encoding the structure of chemicals by molecular descriptors is a crucial step in quantitative structure-activity/property relationships (QSAR/QSPR) modeling. Since ionic liquids (ILs) are disconnected structures, various ways of representing their structure are used in the QSAR studies: the models can [...] Read more.
The process of encoding the structure of chemicals by molecular descriptors is a crucial step in quantitative structure-activity/property relationships (QSAR/QSPR) modeling. Since ionic liquids (ILs) are disconnected structures, various ways of representing their structure are used in the QSAR studies: the models can be based on descriptors either derived for particular ions or for the whole ionic pair. We have examined the influence of the type of IL representation (separate ions vs. ionic pairs) on the model’s quality, the process of the automated descriptors selection and reliability of the applicability domain (AD) assessment. The result of the benchmark study showed that a less precise description of ionic liquid, based on the 2D descriptors calculated for ionic pairs, is sufficient to develop a reliable QSAR/QSPR model with the highest accuracy in terms of calibration as well as validation. Moreover, the process of a descriptors’ selection is more effective when the possible number of variables can be decreased at the beginning of model development. Additionally, 2D descriptors usually demand less effort in mechanistic interpretation and are more convenient for virtual screening studies. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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17 pages, 4280 KiB  
Article
Silica Gel Impregnated by Deep Eutectic Solvents for Adsorptive Removal of BTEX from Gas Streams
by Patrycja Makoś, Edyta Słupek and Aleksandra Małachowska
Materials 2020, 13(8), 1894; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13081894 - 17 Apr 2020
Cited by 22 | Viewed by 3359
Abstract
The paper presents the preparation of new adsorbents based on silica gel (SiO2) impregnated with deep eutectic solvents (DESs) to increase benzene, toluene, ethylbenzene, and p-xylene (BTEX) adsorption efficiency from gas streams. The DESs were synthesized by means of choline chloride, [...] Read more.
The paper presents the preparation of new adsorbents based on silica gel (SiO2) impregnated with deep eutectic solvents (DESs) to increase benzene, toluene, ethylbenzene, and p-xylene (BTEX) adsorption efficiency from gas streams. The DESs were synthesized by means of choline chloride, tetrapropylammonium bromide, levulinic acid, lactic acid, and phenol. The physico-chemical properties of new sorbent materials, including surface morphology and structures, as well as porosity, were studied by means of thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller analysis. The effect of DESs type, flow rate, and initial concentration of BTEX were also investigated followed by regeneration and reusability of adsorbents. The results indicate that SiO2 impregnated with tetrapropylammonium bromide and lactic acid in a 1:2 molar ratio have great potential for the removal of BTEX from gas streams. Its adsorption capacity was higher than the pure SiO2 and other developed SiO2-DES adsorbents. This result can be explained by the specific interaction between DESs and BTEX, i.e., hydrogen bonds interaction. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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13 pages, 1770 KiB  
Communication
Compatibilization Effect of Ionic Liquid-Based Surfactants on Physicochemical Properties of PBS/Rice Starch Blends: An Initial Study
by Ahmad Adlie Shamsuri and Siti Nurul Ain Md. Jamil
Materials 2020, 13(8), 1885; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13081885 - 17 Apr 2020
Cited by 17 | Viewed by 2300
Abstract
Polybutylene succinate (PBS)/rice starch (RS) blends were prepared via the hot-melt extrusion technique through the usage of a twin-screw extruder without and containing ionic liquid-based surfactants (ILbS). Two types of ILbS were used, specifically, 1-dodecyl-3-methylimidazolium trifluoromethanesulfonate, [C12mim][OTf] and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C [...] Read more.
Polybutylene succinate (PBS)/rice starch (RS) blends were prepared via the hot-melt extrusion technique through the usage of a twin-screw extruder without and containing ionic liquid-based surfactants (ILbS). Two types of ILbS were used, specifically, 1-dodecyl-3-methylimidazolium trifluoromethanesulfonate, [C12mim][OTf] and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C12mim][NTf2] were mixed into the PBS/RS blends at the different contents (0–8 wt.%). The tensile and flexural results showed that the blends containing ILbS have a high tensile extension and tensile energy compared to the blend without ILbS. The blends containing ILbS also have a high flexural extension compared with the blend without ILbS. The blends containing [C12mim][NTf2] have a significant improvement in the tensile energy (up to 239%) and flexural extension (up to 17%) in comparison with the blends containing [C12mim][OTf]. The FTIR spectra demonstrated that the presence of ILbS in the blends generated the intermolecular interactions (ion-dipole force and hydrophobic-hydrophobic interaction) between PBS and RS. The DSC results exhibited that the melting points of the prepared blends are decreased with the addition of ILbS. However, the TGA results showed that the thermal decomposition of the blends containing ILbS are higher than the blend without ILbS. The values of decomposition temperature were 387.4 °C, 381.8 °C, and 378.6 °C of PBS/RS-[C12mim][NTf2], PBS/RS-[C12mim][OTf], and PBS/RS, respectively. In conclusion, the ILbS could significantly improve the physicochemical properties of the PBS/RS blends by acting as a compatibilizer. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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Review

Jump to: Research

26 pages, 5596 KiB  
Review
Potential Application of Ionic Liquids for Electrodeposition of the Material Targets for Production of Diagnostic Radioisotopes
by Maciej Chotkowski, Damian Połomski and Kenneth Czerwinski
Materials 2020, 13(22), 5069; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13225069 - 10 Nov 2020
Cited by 7 | Viewed by 2906
Abstract
An overview of the reported electrochemistry studies on the chemistry of the element for targets for isotope production in ionic liquids (ILs) is provided. The majority of investigations have been dedicated to two aspects of the reactive element chemistry. The first part of [...] Read more.
An overview of the reported electrochemistry studies on the chemistry of the element for targets for isotope production in ionic liquids (ILs) is provided. The majority of investigations have been dedicated to two aspects of the reactive element chemistry. The first part of this review presents description of the cyclotron targets properties, especially physicochemical characterization of irradiated elements. The second part is devoted to description of the electrodeposition procedures leading to obtain elements or their alloys coatings (e.g., nickel, uranium) as the targets for cyclotron and reactor generation of the radioisotopes. This review provides an evaluation of the role ILs can have in the production of isotopes. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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19 pages, 3159 KiB  
Review
The Importance of Ionic Liquids in the Modification of Starch and Processing of Starch-Based Materials
by Sylwia Ptak, Arkadiusz Zarski and Janusz Kapusniak
Materials 2020, 13(20), 4479; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13204479 - 9 Oct 2020
Cited by 21 | Viewed by 3091
Abstract
The main applications of ionic liquids in chemistry and material research on one of the most important natural polymers—starch—are presented in this review. A brief characterization of ionic liquids and the advantages and disadvantages of using them in the modification and processing of [...] Read more.
The main applications of ionic liquids in chemistry and material research on one of the most important natural polymers—starch—are presented in this review. A brief characterization of ionic liquids and the advantages and disadvantages of using them in the modification and processing of polysaccharides is presented. The latest reports on the use of various ionic liquids as solvents or co-solvents; as media for synthesizing starch derivatives in oxidation, etherification, esterification, and transesterification, with particular emphasis on biocatalyzed reactions; and as plasticizers or compatibilizers in the processing of starch-based polymers have been investigated. The current trends, possibilities, and limitations of using this type of compound for the production of functional starch-based materials are presented. Full article
(This article belongs to the Special Issue Properties and Applications of Ionic Liquids)
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