• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.583-588
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• 2010

Esterification of free fatty acid with methanol to biodiesel was investigated in a batch reactor using various solid acid catalysts, such as polymer cation-exchanged resins with sulfuric acid functional group(Amberlyst-15, Dowex 50Wx8), acidic ionic liquids (ILs)-modified silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-[ASBI][HSO_4]$, $SiO_2-[ASCBI][HSO_4]$) and grafted silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-R-SO_3H$, $SiO_2-R-SO_2Cl$). The effects of reaction time, temperature, reactant concentration(molar ratio of methanol to oleic acid), and catalyst amount were studied. Allylimidazolium-based ILs on modified silica gels were superior to other tested solid acid catalysts. Especially, the performance of $SiO_2-[ASBI][HSO_4]$ (immobilized by grafting of 3-allyl-1-(4-sulfobutyl)imidazolium hydrogen sulfate on silica gel) was better than that of a widely known Amberlyst-15 catalyst at the same reaction conditions. A high conversion yield of 96% was achieved in the esterification reaction of the simulated cooking oil at 353 K for 2 h. The high catalytic activity of $SiO_2-[ASBI][HSO_4]$ was attributed to the presence of strong Brønsted acid sites from the immobilized functional groups. The catalyst was recovered and the biodiesel product was separated by simple processes such as decantation and filtration.

• Applied Chemistry for Engineering
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• v.27 no.1
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• pp.86-91
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• 2016

Three amorphous silicas and SBA-15 were employed as supports, which were capable of confining ionic liquid (IL) and metallocene in the nanopore. Ionic liquid functionalized silica was prepared by the interaction between the chloride anions of 1,3-bis(cyanomethyl)imidazolium chloride and the surface OH groups. Metallocene and methylaluminoxane (MAO) were subsequently immobilized on the ionic liquid functionalized silica for ethylene polymerization. The metallocene supported on ionic liquid functionalized XPO-2412 and XPO-2410 having a larger pore diameter compared to SBA-15 showed higher activity than that of using supported catalyst without ionic liquid functionalization. However, the activity of metallocene supported on SBA-15 decreased after ionic liquid functionalization, suggesting that the diffusion of ethylene monomer and cocatalyst to the active site of nanopore was restricted during ethylene polymerization. This could be resulted from significant reduction of the pore diameter due to the immobilization of ionic liquid and $(n-BuCp)_2ZrCl_2$ and MAO. The effect on polymerization activity in accordance with the concentration of hydroxyl groups on the surface was also investigated. The polymerization activity increased as the concentration of hydroxyl groups on amorphous silica increased. The polymerization activities of metallocene supported on silica showed the similar trend after ionic liquid functionalization.

• Korean Chemical Engineering Research
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• v.58 no.1
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• pp.44-51
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• 2020

The basic catalyst 1-benzyl-3-methyl-imidazolium hexafluoroantimonate (BMH) was synthesized and analyzed by FT-IR and ¹H-NMR. A crystalized biphenyl-based epoxy was synthesized by using tetramethyl biphenol (TMBP) and epichlorohdrine. In order to consider the curing tendency of the synthesized BMH, the mass ratio was changed to 0.5, 1.0, 2.0 wt.% under heated conditions and the curing tendency was analyzed by differential scanning calorimeter (DSC). As a result, the BMH catalyst showed a fast curing result in the stepwise heating pr℃ess of the biphenol-A epoxy and the cationic polymer. From these results, the BMH catalyst showed excellent thermal stability as a potential heat curing catalyst. In addition, we considered the application possibility of epoxy molding compound (EMC) which required a skeleton structure and a high heat resistance because the synthesized biphenyl epoxy had a characteristic of rapidly lowering viscosity at a constant temperature and a rigid skeleton structure of biphenol. As a result, it was confirmed that the TMBP-based epoxy developed in this study was composed of a crystalline structure, and a curing reaction was observed with a Novolac resin at a high temperature. In the presence of a catalyst, a curing reaction was observed around 150 ℃ and thus TMBP-based epoxy was successfully applied as a raw material of EMC.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.80.2-80.2
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• 2010

The development of high temperature-proton exchange fuel cell (HT-PEFC) is a key in solving the problem of carbon monoxide poisoning of the platinum at anode as well as water management in PEFCs operated below $90^{\circ}C$. In order to overcome these main issues, PEFCs must be operated at high temperature above $120^{\circ}C$. Ionic liquids are available for HT-PEFC due to exhibiting non-volatility and thermal stability. Ionic liquids are however leached out from polymeric matrix resulting in the increase of gas permeability. In this study, we have prepared and characterized the composite membranes with the ionic liquids consisting of 1-(4-vinylbenzyl)-3-butyl imidazolium chloride immobilized by the cross-linkers in pore-filling membrane to prevent to be leached out from the membrane. We confirmed that cross-linked ionic liquids were not leached out from the composite membranes through the various characteristic analyses. It was also verified that the prepared membranes are thermally stable from the result of TG analysis. The pore-filling membranes with the immobilized ionic liquids have a high proton conductivity over $10^{-2}$ S/cm at high temperature (> $120^{\circ}C$).

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3373-3377
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• 2012

A series of polystyrene-supported 1-(propyl-3-sulfonate)-3-methyl-imidazolium hydrosulfate acidic ionic liquid (PS-$[SO_3H-PMIM][HSO_4]$) catalysts were prepared and tested for mononitration of simple aromatics compounds with nitric acid. It was found that the reactivity of the catalysts increased with increasing $[SO_3H-PMIM][HSO_4]$ content. The para-selectivity was not only related to the $[SO_3H-PMIM][HSO_4]$ content but also the substituent groups in aromatics. A reaction mechanism of nitration over this new catalyst was proposed. The catalytic activity of this catalyst decreased slightly after fifth runs in the synthesis of nitrotoluene.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2489-2493
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• 2012

A new fluorescent system (acridine/RTIL hybrid gel) confined in the 3D micro-structure of a poly(lactic acid) membrane were prepared from 1-butyl-3-methylimidazolium-based ionic liquids ([bmim]X (X = $SbF_6$, $NTf_2$, Cl); RTILs), poly(lactic acid) (PLA), and acridine via the sol-gel route. SEM images showed that, in the presence of [bmim]$SbF_6$ and [bmim]$NTf_2$, 3D-ly paticulated structures were created inside the PLA membranes and acridine/RTIL hybrid gels were confined in gabs of particulates. However, the use of [bmim]Cl induced the formation of a 3D-ly porous structure containing the hybrid gel of acridine/[bmimCl in the micropores. The three fluorescent systems exhibited different fluorescence behaviors (fluorescence maximum and intensity) depending on the C2-H acidity scale of the RTILs (or their anion type). Acridine gels hybridized with [bmim]$SbF_6$ and [bmim]$NTf_2$ showed blue fluorescence with relative high intensity, whereas the hybrid gel with [bmim]Cl exhibited almost no fluorescence under dry conditions. However, the acridine/[bmim]Cl hybrid system in the micro-porous PLA membrane started to emit fluorescent light under humid conditions and showed a possible response, indicating that it could be applied as a humidity sensor.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2679-2683
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• 2014

Mechanisms underlying the impacts of interactions between carbon nanoparticles (CNPs) and ionic liquids (ILs) on the physicochemical behavior of CNPs need to be more full worked out. This manuscript describes a theoretical investigation at multiple levels on the interactions of fullerene $C_{60}$ with 21 imidazolium-based ILs of varying alkyl side chain lengths and anionic types and their impacts on $C_{60}$ dispersion behavior. Results show that ${\pi}$-cation interaction contributed to mechanism of the $C_{60}$-IL interaction more than ${\pi}$-anion interaction. The calculated interaction energy ($E_{INT}$) indicates that $C_{60}$ can form stable complex with each IL molecule. Moreover, the direction of charge transfer occurred from IL to $C_{60}$ during the $C_{60}$-IL interaction. Quantitative models were developed to evaluate the self-diffusion coefficient of $C_{60}$ ($D_{fullerene}$) in bulk ILs. Three interpretative molecular descriptors (heat of formation, $E_{INT}$, and charge) that describe the $C_{60}$-IL interactions and the alkyl side chain length were found to be determinants affecting $D_{fullerene}$.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.2058-2062
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• 2011

The effect of the addition of ionic liquids with four different cations (imidazolium, pyrrolidinium, piperidinium and pyridinium) on the performance of dye-sensitized $TiO_2$ solar cells based on electrolytes containing a t-butylpyridine (TBP) in 3-methoxypropionitrile (MPN) was studied. A total of 18 ionic liquids with mono-, di- and tri-alkyl derivatives were used in the present study, and among them a pyridinium cation with a mono-alkyl group showed better cell efficiency than the others. The best photoelectric conversion efficiency, 7.213%, was obtained using 1-hexylpyridinium iodide with an open-circuit photovoltage ($V_{oc}$) = 0.731 V, a short-circuit photocurrent density ($J_{sc}$) = 16.175 $mA/cm^2$, and a fill factor (ff) = 0.610 under AM1.5 and 100 $mW/cm^2$ illumination.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1873-1878
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• 2011

Under solvent-free conditions and in one-pot, a series of 2-amino-4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-pyridines and 4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-2(1H)-pyridinones were prepared using 3,4-dimethoxyacetophenone, an aldehyde, malononitrile (or ethyl cyanoacetate), and ammonium acetate in the presence of 3-methyl-1-(4-sulfonylbutyl)imidazolium hydrogen sulfate $[HO_3S(CH_2)_4MIM][HSO_4]$ (a Br${\o}$nsted acidic ionic liquid) as the catalyst in very short reaction time. The preference for the formation of more stable tautomers was consistence with the theoretical calculation using the Gaussian 03 program at the B3LYP hybrid density functional level.

• Journal of the Korea Institute of Military Science and Technology
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• v.16 no.5
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• pp.690-702
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• 2013

Ionic liquids(ILs) have been the most investigated chemicals among green solvents including water, glycerol, supercritical carbon dioxdie($scCO_2$). ILs are attracting organic as well as inorganic chemicals because most ionic liquids' vapor pressures are very low so that ILs are liquids phase at ambient conditions. ILs are composed of various anions and cations, thus chemists can design functionalized solvents and/or catalysts that can be used in specific synthetic reactions by means of combinations of different ions. Many scientists believe ILs being green materials because of its low vapor pressure as well as the flexibility in controlling the chemical and physical properties. In this review the author describes recent development of ILs focused on imidazolium and pyridinium ILs which are being most investigated presently. In order to apply this materials in industrial level, the toxicity matter must be resolved first. In this regard, the author describes recent research trend regarding environmental effects by ILs as well as some meaningful results as well.