• Clean Technology
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• v.24 no.3
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• pp.190-197
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• 2018

Various waterborne polyurethanes (WPU) with three different types of polyol such as ester type polyol [adipic acid (A)/BD/3-methyl-1,5-pentandiol (MPD) and A/BD]//carbonate type polyol (C/HD/MPD, C/HD, C/BD)//ether type polyol (PTMG) were prepared in this study. This study focused on the effect of polyol type on the properties of WPU. Soft segment Tg (Tgs), 100% elastic modulus and tensile strength were highest when using carbonate polyol, followed by ester polyol and ether polyol, while those of elongation showed the opposite trend. The WPU synthesized with MPD - containing polyol showed lower Tgs, 100% elasticity and strength, and higher elongation than MPD - free WPU. The % transmittance and transparency of the WPU film containing the MPD component was superior to that of the WPU film containing no MPD component, and it was found that the film based on carbonate polyol was slightly better than the film based on ester polyol and ether polyol.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.217-222
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• 2012

The synthesis of dimethyl carbonate(DMC) is a promising reaction for the use of naturally abundant carbon dioxide. DMC has gained considerable interest owing to its versatile chemical reactivity and unique properties such as high oxygen content, low toxicity, and excellent biodegradability. In this study, the synthesis of DMC through the transesterification of ethylene carbonate(EC) with methanol was investigated by using ionic liquid and metal oxide catalysts. The screening test of different catalysts revealed that choline hydroxide ([Choline][OH]) and 1-n-butyl-3-methyl imidazolium hydroxide([BMIm][OH]) had better catalytic performance than metal salts catalysts such as MgO, ZnO and CaO. The effects of reaction parameters such as reaction temperature, MeOH/EC mole ratio, and carbon dioxide pressure on the reactivity of [Choline][OH] catalyst were discussed. High temperature and high MeOH/EC mole ratio were favorable for high conversion of EC. However, the yield of DMC showed a maximum when carbon dioxide pressure was 1.34 MPa, and then it decreased for higher carbon dioxide pressure. Zinc chloride($ZnCl_2$) was used as co-catalyst with the ionic liquid catalyst. The mixed catalyst showed a synergy effect on the EC conversion and DMC yield probably due to the acid-base properties of the catalysts.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.5 no.5
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• pp.480-483
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• 2004

Butylene carbonate(4-ethyl-l,3-dioxolan-2-one), one of the cyclic carbonate was synthesized by the thermal degradation of poly(butylene carbonate). The poly(butylene carbonate) was made from 1,2-Epoxybutane and carbon dioxide which is one of the main green house gas. The prepared cyclic carbonate was identified by GC-Mass. This synthetic method is an alternative way to prepare cyclic carbonates.

• Clean Technology
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• v.22 no.1
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• pp.35-44
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• 2016

In this study, a computational chemistry methodology called as molecular modeling was been applied to explain several experiment results mechanistically. The reaction chosen for this study was to remove carbon dioxide, known as a primary greenhouse gas, by an epoxide via the carbon dioxide fixation to produce carbonates. This reaction inherently needs the use of catalysts because it has a significantly high activation barrier (55~59 kcal/mol). Among various types of catalysts, we studied in zeolitic imidazolate framework 90 (ZIF-90)/ionic liquid immobilized ZIF-90 (IL-ZIF-90), polystyrene-supported quaternized ammonium salt, KI/KI-glycine, and dimethylethanolamine (DMEA). First, probable reaction pathways were proposed based on calculated energetics by computational chemistry. The energetics was then used for the thermodynamic interpretation on the activity of catalysts. In the case of ZIF-90/IL-ZIF-90 and KI/KI-glycine, IL-ZIF-90 and KI-glycine showed better yields compared to their counterparts. The calculation proposed interesting results that it is not from the lowering of activation energy but from the unstable intermediates of ZIF-90 and KI-glycine. For DMEA, the calculated activation energy was ~42 kcal/mol, much lower than that of the non-catalytic reaction. A possible reaction pathway was located to confirm the interaction between −NH group from ammonium and oxygen from epoxide for polystyrene-supported quaternized ammonium salt.

• Clean Technology
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• v.19 no.4
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• pp.416-422
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• 2013

In environmental friendly aspects, the synthesis of glycerol carbonate from glycerol using carbon monoxide and oxygen gases which were produced in petrochemical plants was studied. The oxidative carbonylation of glycerol under batch reaction system was performed on parameter conditions such as effect of various metals (Cu, Pd, Fe, Sn, Zn, Cr), oxidizing agents, mole ratio of carbon monoxide to oxygen, catalyst amount, solvent types, reaction temperature and time and dehydrating agents. In particular copper chloride catalysts showed the excellent activities, and the glycerol carbonate yields over CuCl and $CuCl_2$ catalysts were the maximum of 44% and 64%, respectively at the following reaction conditions: solvent as nitrobenzene, mole ratio of 1:3:0.15 (glycerol:carbon monoxide:catalyst), mole ratio of 2:1 (carbon monoxide:oxygen), the total pressure of 30 bar at 413 K for 4 hr. It was found that reactivity were significantly different depending on the oxidation number of Cu catalysts, and oxygen plays an important role as oxidizing agents in producing H2O during oxidation reaction after carbonylation of glycerol.

• Journal of the Korean Chemical Society
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• v.50 no.2
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• pp.129-136
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• 2006

Synthesis of novel polymeric ligands based on myo-inositol was performed. Cyclopolymerization, whose mechanism and the cyclic structure were proved, was first attempted to build a conformationally rigid inositol polymer. Comparative spectroscopic methods were introduced to verify the conformation of the prepared cyclohexane polymers. A conformationally rigid polymeric ligand was successfully prepared using myo-inositol carbonate.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.621-626
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• 2010

In this study, imidazole-based ionic liquid on polystyrene was prepared and its catalytic performance in the cycloaddition of $CO_2$ with allyl glycidyl ether(AGE) to produce allyl glycidyl carbonate was investigated. The ionic liquid was generated on the polystyrene-based polymer through the immobilization of imidazole. The prepared catalyst was characterized using a number of instrumental analysis including EA, FT-IR, TGA and SEM. The immobilized ionic liquid showed very good catalytic activity for the cycloaddition of $CO_2$ with AGE, having 80% of AGE conversion with over 96% of the carbonate selectivity at $120^{\circ}C$ under 1.48 MPa $CO_2$ pressure. The immobilized ionic liquid can be used for the reaction up to four consecutive runs without significant loss of its catalytic activity.

• Applied Chemistry for Engineering
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• v.9 no.2
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• pp.273-277
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• 1998

The synthesis of hydroxy-terminated poly(propylene carbonate)(HTPPC) was performed by the reaction of propylene carbonate(PC) with alcohol initiator using metal alkoxides, crown ethers and quaternary onium salts as catalysts. The effects of catalyst structure, types and concentration of alcohol, and solvent were investigated. Among the alkoxide catalysts tested, the ones with higher Lewis acidity and with more nucleophilic alkoxide anion showed higher catalytic activity. Mixed catalysts of metal alkoxied and crown ether showed higher conversion of PC than metal alkoxide alone. Quaternary onium salts of bulky cation exhibited higher catalytic activity. High polar solvent showed higher yield of HTPPC and the yield increased with the decrease of [PC]/[Initiator] ratio.

• Applied Chemistry for Engineering
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• v.27 no.2
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• pp.153-157
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• 2016

In this study, three different metal-containing ionic liquid catalysts were prepared by metal insertion and characterized by various physicochemical analytic methods. The catalytic performance of the metal containing ionic liquids in the cycloaddition of $CO_2$ with propylene oxide (PO) to produce propylene carbonate (PC) was investigated under the solvent free condition. The order of approximate rate constants ($K_{app}$) for the metal containing ionic liquid catalysts was $(MeIm)_2ZnCl_2$, > $(MeIm)_2FeCl_2$ > $(MeIm)_2CuCl_2$. These results are in accord with the experimentally obtained activity order of the different metal containing ionic liquid catalysts.

• Polymer(Korea)
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• v.33 no.2
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• pp.175-182
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• 2009

Waterborne polyurethanes (WPUs) based on isophorone diisocyanate and mixed polyols of poly(tetramethylene glycol) (PTMG)/polycarbonate diol (PCD) were synthesized. The variation of mechanical and dyeing properties and alkali resistance of the WPU films were analyzed according to the polycarbonate (PC) content. The tensile strength of the films increased and the elongation at break decreased with the PC content in the WPU film. The incorporation of PC component in the WPU film did not affect the alkaline hydrolysis behavior. The synthesized WPU solutions were used as impregnating resins for the production of PET artificial leathers. The prepared WPU resins showed the good color fastness to washing, rubbing, and light of the artificial leather fabrics. The improvement of the properties became greater with the PC content in the WPU resin.