30345-49-4Relevant academic research and scientific papers
High-Performance Porous Ionic Liquids for Low-Pressure CO2 Capture**
Avila, Jocasta,Chung Szeto, Kai,Costa Gomes, Margarida,Denis-Quanquin, Sandrine,Lepre, L. Fernando,Padua, Agilio A. H.,Santini, Catherine C.,Tiano, Martin
, p. 12876 - 12882 (2021)
Porous ionic liquids are non-volatile, versatile materials that associate porosity and fluidity. New porous ionic liquids, based on the ZIF-8 metal–organic framework and on phosphonium acetate or levulinate salts, were prepared and show an increased capacity to absorb carbon dioxide at low pressures. Porous suspensions based on phosphonium levulinate ionic liquid absorb reversibly 103 % more carbon dioxide per mass than pure ZIF-8 at 1 bar and 303 K. We show how the rational combination of MOFs with ionic liquids can greatly enhance low pressure CO2 absorption, paving the way towards a new generation of high-performance, readily available liquid materials for effective low pressure carbon capture.
Application of mild autohydrolysis to facilitate the dissolution of wood chips in direct-dissolution solvents
Deb, Somdatta,Labafzadeh, Sara R.,Liimatainen, Unna,Parviainen, Arno,Hauru, Lauri K. J.,Azhar, Shoaib,Lawoko, Martin,Kulomaa, Tuomas,Kakko, Tia,Fiskari, Juha,Borrega, Marc,Sixta, Herbert,Kilpel?inen, Ilkka,King, Alistair W. T.
, p. 3286 - 3294 (2016)
Wood is not fully soluble in current non-derivatising direct-dissolution solvents, contrary to the many reports in the literature quoting wood 'dissolution' in ionic liquids. Herein, we demonstrate that the application of autohydrolysis, as a green and economical wood pre-treatment method, allows for a massive increase in solubility compared to untreated wood. This is demonstrated by the application of two derivitising methods (phosphitylation and acetylation), followed by NMR analysis, in the cellulose-dissolving ionic liquids 1-allyl-3-methylimidazolium chloride ([amim]Cl) and 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]). In addition, the non-derivitising tetrabutylphosphonium acetate ([P4444][OAc]) : DMSO-d6 electrolyte also allowed for dissolution of the autohydrolysed wood samples. By combination of different particle sizes and P-factors (autohydrolysis intensity), it has been clearly demonstrated that the solubility of even wood chips can be drastically increased by application of autohydrolysis. The physiochemical factors affecting wood solubility after autohydrolysis are also discussed.
Amphiphilic and phase-separable ionic liquids for biomass processing
Holding, Ashley J.,Heikkilae, Mikko,Kilpelaeinen, Ilkka,King, Alistair W. T.
, p. 1422 - 1434 (2014)
One main limiting factor for the technoeconomics of future bioprocesses that use ionic liquids (ILs) is the recovery of the expensive and potentially toxic IL. We have demonstrated a new series of phase-separable ionic liquids, based on the hydrophobic tetraalkylphosphonium cation ([PRRRR] +), that can dissolve lignin in the neat state but also hemicellulose and high-purity cellulose in the form of their electrolyte solutions with dipolar aprotic solvents. For example, the IL trioctylmethylphosphonium acetate ([P8881][OAc]) was demonstrated to dissolve up to 19 wt % of microcrystalline cellulose (MCC) at 60 °C with the addition of 40 wt % of DMSO. It was found that the MCC saturation point is dependent on the molar ratio of DMSO and IL in solution. At the optimum saturation, a ～1:1 molar ratio of [P8881][OAc] to anhydroglucose units is observed, which demonstrates highly efficient solvation. This is attributed to the positive contribution that these more amphiphilic cation-anion pairs provide, in the context of the Lindman hypothesis. This effective dissolution is further illustrated by solution-state HSQC NMR spectroscopy on MCC. Finally, it is also demonstrated that these electrolytes are phase separable by the addition of aqueous solutions. The addition of 10 % NaOAc solution allows a near quantitative recovery of high-purity [P8881][OAc]. However, increased volumes of aqueous solution reduced the recovery. The regenerated material was found to partially convert into the cellulose II crystalline polymorph. Solving the dissolving: Hydrophobic wood-biopolymer-solvating ionic liquids are developed that are phase separable from aqueous solutions as a means of recycling. These ionic liquids are excellent solvents for cellulose in the form of their DMSO electrolyte solutions but only dissolve lignin as the pure ionic liquids.
Synergistic catalysis of imidazole acetate ionic liquids for the methanolysis of spiral poly(ethylene 2,5-furandicarboxylate) under a mild condition
Qu, Xiaoling,Zhou, Guangyuan,Wang, Rui,Yuan, Bolei,Jiang, Min,Tang, Jun
, p. 1871 - 1882 (2021/03/09)
Alcoholysis is a potential method for the degradation of polyesters to their precursor building blocks, which can then be polymerized again to form new qualified polyester materials. This method therefore makes recycling possible in a permanent polymer-monomer-polymer loop. In this study, a series of metal-free tetrabutylphosphonium-based ionic liquids (ILs) were prepared as catalysts for the methanolysis of poly(ethylene 2,5-furandicarboxylate) (PEF), which is well known as an ideal alternative to the petroleum-based plastic poly(ethylene terephthalate) (PET). It was found that anions with stronger electronegativity were more efficient for the methanolysis of PEF. By adjusting the structures of the anions and cations of ILs, 1-butyl-3-methylimidazole acetate ([BMIm][OAc]) exhibited excellent catalytic activity in the methanolysis of PEF. The optimization of reaction parameters enabled the [BMIm][OAc]-catalyzed methanolysis of PEF with nearly 100% PEF degradation and a 77.6% dimethyl furan-2,5-dicarboxylate (DMFD) yield at 130 °C for 30 min. Furthermore, [BMIm][OAc] could keep high-activity after using for six times under the optimum conditions. Assisting with1H NMR, FT-IR and density functional theory (DFT) calculations, an in-depth study was performed on the feasible synergetic catalytic mechanism of [BMIm][OAc] for the methanolysis of PEF, induced by hydrogen bonds formed between reactants and [BMIm][OAc]. Finally, on the basis of experimental results and scanning electron microscopy (SEM), it was confirmed that PEF with the spiral motif could be degraded under milder conditions than PET. Therefore, this strategy of using adjustable cation and anion structures in ILs provides an opportunity to develop other more efficient ILs for the alcoholysis of furan-based polymersviaa green and mild pathway.
Encapsulated Amino-Acid-Based Ionic Liquids for CO2 Capture
Silva, Liliana P.,Moya, Cristian,Sousa, Marco,Santiago, Ruben,Sintra, Tania E.,Carreira, Ana R. F.,Palomar, José,Coutinho, Jo?o A. P.,Carvalho, Pedro J.
supporting information, p. 3158 - 3166 (2020/08/10)
Ionic liquids have gathered special attention due to their potential for carbon dioxide capture, and their potential as solvents for mitigation of climate change. Following the scope of previous works, amino-acid-based ionic liquids encapsulated (ENILs) into carbonaceous submicrocapsules are here proposed as a novel material for CO2 capture. The ENILs prepared using tetrabutylphosphonium acetate ([P4,4,4,4][Ac]), used as reference, (2-hydroxyethyl)trimethylammonium l-phenylalaninate ([N1,1,1,2(OH)][L-Phe]), (2-hydroxyethyl)trimethylammonium l-prolinate ([N1,1,1,2(OH)][L-Pro]), and tetrabutylammonium l-prolinate ([N4,4,4,4][L-Pro]) were characterized by SEM, TEM, elemental analysis, TGA, and BET to assess their morphology, chemical composition, porous structure, and thermal stability. The absorption of CO2 on these materials was studied up to 0.5 MPa and 343 K. The desorption of CO2 from the saturated ENILs was evaluated, under mild conditions, evidencing these materials as promising agents for CO2 capture from post-combustion sources, with high sorption capacity and fast and complete regeneration.
Ligand-free copper(i) oxide nanoparticle-catalysed amination of aryl halides in ionic liquids
Kessler, Michael T.,Robke, Silas,Sahler, Sebastian,Prechtl, Martin H. G.
, p. 102 - 108 (2014/01/06)
In the following, we present a simple and feasible methodology for a C-N coupling reaction using nanoscale Cu2O catalysts incorporated in n-Bu4POAc ionic liquid media. It is shown that a wide range of amines and aryl halides can be coupled selectively in high yields, without the use of ligands or additives (bases) and without precautions against water or air. All catalyses can be carried out with a nanoparticle catalyst loading as low as 5 mol%, based on the used precursor.
Recyclable nanoscale copper(I) catalysts in ionic liquid media for selective decarboxylative C-C bond cleavage
Kessler, Michael T.,Gedig, Christian,Sahler, Sebastian,Wand, Patricia,Robke, Silas,Prechtl, Martin H. G.
, p. 992 - 1001 (2013/04/24)
Here we report the synthesis and application of finely divided Cu 2O nanoparticles (Cu2O-NPs) in the range from 5.5 nm to 8.0 nm in phosphonium ionic liquids as the first recyclable and effective catalytic system for smooth, ligand- and additive-free protodecarboxylation of 2-nitrobenzoic acid as a model substrate and further derivatives. The reactions run with low catalyst loadings and result in quantitative yield in ten consecutive recycling experiments. In addition this system is highly selective towards electron-poor 2-nitrobenzoic acids.
PEG-functionalized ionic liquids for cellulose dissolution and saccharification
Tang, Shaokun,Baker, Gary A.,Ravula, Sudhir,Jones, John E.,Zhao, Hua
, p. 2922 - 2932,11 (2012/12/12)
Cellulose-dissolving ionic liquids (ILs) have become powerful neoteric solvents in the pretreatment of cellulosic biomass for ethanol fuel production. There are, however, a number of challenges to using current ionic solvents at large scales (imidazolium-based salts, in particular), including their relatively high costs and viscosities and their sluggish biodegradability. Aiming to overcome these hurdles, we have prepared a new series of poly(ethylene glycol) (PEG)-functionalized ILs comprising inexpensive alkylammonium or piperidinium cations paired with acetate anions. Some of these new ILs are capable of dissolving 8-12 wt% cellulose, while displaying low viscosities and acceptable thermal stabilities at the required process temperature. Our XRD and SEM data further confirm that regenerative pretreatment of cellulose by these PEGylated ILs can effectively transform the cellulose I structure to cellulose II, reducing the crystallinity of cellulose and increasing the structural homogeneity. Most excitingly, cellulose regenerated from these ILs can be rapidly hydrolyzed to glucose, in ～90% glucose yield after 2 h, using a commercial cellulase supplemented with β-glucosidase.
ISOCYANATE TRIMERISATION CATALYST SYSTEM, A PRECURSOR FORMULATION, A PROCESS FOR TRIMERISING ISOCYANATES, RIGID POLYISOCYANURATE/POLYURETHANE FOAMS MADE THEREFROM, AND A PROCESS FOR MAKING SUCH FOAMS
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, (2011/09/14)
The instant invention provides an isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid foams made therefrom, and a process for making such foams. The trimerisation catalyst system comprises: (a) a phosphonium cation; and (b) an isocyanate-trimer inducing anion; wherein said trimerisation catalyst system has a trimerisation activation temperature in the range of equal to or less than 73° C. The precursor formulation comprises (1) at least 25 percent by weight of polyol, based on the weight of the precursor formulation; (2) less than 15 percent by weight of a trimerisation catalyst system, based on the weight of the precursor formulation, comprising; (a) a phosphonium cation; and (c) an isocyanate-timer inducing anion; wherein said trimerisation catalyst system has a trimerisation activation temperature in the range of equal to or less than 73° C.; and (3) optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more auxiliary blowing agents, one or more urethane catalysts, one or more auxiliary trimerisation catalysts, or combinations thereof. The process for trimerisation of isocyanates comprises the steps of: (1) providing one or more monomers selected from the group consisting of an isocyanate, a diisocyanate, a triisocyanate, oligomeric isocyanate, a salt of any thereof, and a mixture of any thereof; (2) providing a trimerisation catalyst system comprising; (a) an phosphonium cation; and (b) an isocyanate-trimer inducing anion; (c) wherein said trimerisation catalyst system has a trimerisation activation temperature in the range of equal to or less than 73° C.; (3) trimerising said one or more monomers in the presence of said trimerisation catalyst; (4) thereby forming an isocyanurate trimer. The process for making the PIR foam comprises the steps of: (1) providing one or more monomers selected from the group consisting of an isocyanate, a diisocyanate, a triisocyanate, oligomeric isocyanate, a salt of any thereof, and a mixture of any thereof; (2) providing polyol; (3) providing a trimerisation catalyst system comprising; (a) a phosphonium cation; and (b) an isocyanate-trimer inducing anion; wherein said trimerisation catalyst system has a trimerisation activation temperature in the range of equal to or less than 73° C.; and (4) optionally providing one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more auxiliary blowing agents, one or more urethane catalysts, one or more auxiliary trimerisation catalysts, or combinations thereof; (5) contacting said one or more monomers, and said polyol, and optionally said one or more surfactants, and optionally said one or more flame retardants, and optionally said water, and optionally said one or more antioxidants, and optionally said one or more auxiliary blowing agents in the presence of said trimerisation catalyst system and optionally said one or more urethane catalysts, and optionally said one or more auxiliary trimerisation catalysts; (6) thereby forming said polyisocyanurate/polyurethane rigid foam. The PIR foam comprises the reaction product of one or more monomers selected from the group consisting of an isocyanate, a diisocyanate, a triisocyanate, oligomeric isocyanate, a salt of any thereof, and a mixture of any thereof with polyol in the presence of a trimerisation catalyst system comprising a phosphonium cation, and an isocyanate-trimer inducing anion, and optionally one or more surfactants, optionally one or more flame retardants, optionally water, optionally one or more antioxidants, optionally one or more auxiliary blowing agents, optionally one or more additional urethane catalysts, and optionally one or more auxiliary trimerisation catalysts, or optionally combinations thereof, wherein the trimerisation
