• 한국응용과학기술학회지
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• 제9권2호
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• pp.141-148
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• 1992

Transesterification reactions (methyl methacrylate with diethanolamine, ethylene glycol with dimethylphthalate) were kinetically investigated in the presence of zinc compound catalysts at $120{\sim}170^{\circ}C$ The amount of reactants was measured by gas chromatography. and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively, The overall reaction order was 2nd. The apparent rate constant (k') was found to obey first kinetics with respect to the concentration of catalyst. It shows that according to an increase in basicity of anionic species the rate constant increase, and that a linear relationship exists between ln k and pKa in transesterification reaction of methyl methacrylate with diethanolamine.

• Korean Chemical Engineering Research
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• 제56권3호
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• pp.416-420
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• 2018

A comprehensive kinetic study has been conducted on dimethyl carbonate synthesis by transesterification reaction of ethylene carbonate with methanol. An alkali base metal (KOH) was used as catalyst in the synthesis of DMC, and its catalytic ability was investigated in terms of kinetics. The experiment was performed in a batch reactor at atmospheric pressure. The reaction orders, the activation energy and the rate constants were determined for both forward and backward reactions. The reaction order for forward and backward reactions was 0.87 and 2.15, and the activation energy was 12.73 and 29.28 kJ/mol, respectively. Using the general factor analysis in the design of experiments, we analyzed the main effects and interactions according to the MeOH/EC, reaction temperature and KOH concentration. DMC yield with various reaction conditions was presented for all ranges using surface and contour plot. Furthermore, the optimal conditions for DMC yield were determined using response surface method.

• 한국응용과학기술학회지
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• 제7권1호
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• pp.71-76
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• 1990

Transesterification reactions (methyl methacrylate with monoethanolamine, methyl methacrylate with n-butyl alcohol, dimethylphthalate with ethylene glycol, dimethyl phthalate with monoethanolamine) were kinetically investigated in the presense of various metal acetate catalysts at $110^{\circ}C$. The amount of reactants was measured by gas and liquid chromatography, and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively. The overall reaction order was 2nd, Maximum reaction rates were appeared at the range of 1.4 to 1.6 in electronegativity of metal ions and maximum catalytic activities were obserbed at the range of 1.5 to 1,8 in instability constant of metal acetates.

• 한국응용과학기술학회지
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• 제9권1호
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• pp.7-13
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• 1992

Lipases catalyzed the transesterification reaction between esters and various primary and secondary alcohols in a 99% organic medium, porcine pancreatic, yeast, mold lipases can vigorously act as catalysts in a number of nearly anhydrous organic solvents. Various transesterification reactions catalyzed by porcine pancreatic lipase in hexane obey Michaelis-Menten kinetics. The dependence of the catalytic activity of the enzyme in organic media on the pH of the aqueous solution from which it was recovered is bell-shaped, with the maximum coinciding with the pH optimum of the enzymatic activity in water. The catalytic power exhibited by the lipases in organic solvents is comparable to that displayed in water. In addition to transesterification, lipases Can catalyze several other processes in organic media.

• Advances in environmental research
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• 제1권3호
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• pp.191-199
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• 2012

A kinetic study of the transesterification of soybean oil was conducted using microwaves under various temperatures, power densities, and reaction times. Results show that power density affects the kinetics and yield. The biodiesel yield increased with increasing microwave power density. The non-thermal effects of microwave irradiation on transesterification reactions were evaluated at a constant reaction temperature ($65^{\circ}C$) and power density (0.204 $Wg^{-1}$). Microwave irradiation was found to increase the reaction rates by 3.52-7.06 fold.

• 한국진공학회:학술대회논문집
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• 한국진공학회 1999년도 제17회 학술발표회 논문개요집
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• pp.203-203
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• 1999

Mass spectrometry technique provides the molecular weight distribution, data on the sequence of repeat units, polymer additives, and impurities, and structural information. time-of-Flight secondary Ion Mass Spectrometry (TOF-SIMS) has been used for structural characterization of various polymers1-2. the masses of repeat units and terminal groups and molecular weight distributions of polymers have been determined from their TOF-SIMS spectra. TOF-SMIS provides good sensitivity and structural specificity for high mass ions so that intact oligomers and large polymer fragments are observed. In this study, we investigated the detailed structural information on the oligomers and fragment ions of branched poly(1,3-butylene adipate) and branched poly[di(ethylene glycol) adipate] and the transesterification products of branched polyesters with trifluoroacetic acid or chloro difluoroacetic acid. Branched polyesters were chosen because they are important polymers but difficult to characterize; thus branched polyesters provide challanging test for TOF-SIMS. TOF-SIMS spectra of polyesters are obtained from thin polymer films cast from solution on a silver substrate. A good solvent for a polumer solution disrupts intermolecular forces between polymer chains but leaves the polumer intact. Transesterification reactions are potentially useful for characterization of high molecular weight and intractable polyesters. Transesterification products of polyesters and trifluoroacetic acid or an integral number of polyester repeat units and an additional diol. The progress of such reactions was monitored using peak intensities of reactants and products in TOF-SIMS spectra. The increasing abundance of tagged ions indicates that the reaction has progressed with time.

• 대한화학회지
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• 제41권3호
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• pp.157-165
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• 1997

에스테르 교환반응은 고분자 블랜드의 가공시 자체 상용화제를 만들 수 있어 폴리에스테르의 공업적제조에 이용되어질 수 있다. 따라서 에스테르 교환반응에 대한 연구의 일환으로서 열방성 액정고분자인 TR-4,6(poly(tetramethylene-4,4'-terephthaloyldioxydibenzoate-co-hexametylene-4,4'-terephthaloyldioxydibenzoate)를 합성하게 되었으며 이것을 엔지니어링 플라스틱인 폴리부틸렌테레프탈레이트(PBT)와 블랜딩을 하였다. 이 두 구성고분자 사이의 에스테르 교환반응은 IR, DSC, 및 $^{13}C-NMR$에 의한 통계적 처리방법에 의하여 분석하였으며, 교환반응 진행속도와 모노머의 반복단위 서열분포도 조사 연구하였다.

• Korean Chemical Engineering Research
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• 제51권1호
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• pp.58-67
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• 2013

PBT (polybutylene terephthalate)는 저흡수율, 치수 안정성, 내마모성 등 기계적 특성이 우수하며, 전기전자 부품, 자동차 부품, 각종 정밀 부품에 사용된다. DMT (dimethyl terephthalate)와 BD (1,4-butandiol)를 사용하여 PBT의 원료단량체인 BHBT (bis-hydroxybutyle terephthalate)를 생산하는 에스테르 교환 반응 반응에 대해 연구 하였다. 촉매로는 zinc acetate가 사용되었다. 기존의 연구에서는 반응 중 생성 메탄올이 제거되는 반회분식 반응기를 통한 kinetics 연구가 이루어져 역반응이 고려되지 않음에 따른 모델의 부정확함이 있었다. 본 연구에서는 회분식 반응기를 사용하고 반응 중 DMT와 메탄올 양을 정량하여 생성되는 MHBT (methyl hydroxylbutylene terephthalate)와 BHBT를 추정할 수 있도록 하고, 이 반응들에서 역반응들을 고려할 수 있도록 하여 보다 정확한 모델을 제안하였다. 다양한 반응속도 모델을 제시하였고, 이 모델들이 예측한 값들이 실험 데이터와 잘 일치함을 보였다.

• 한국환경과학회지
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• 제19권10호
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• pp.1247-1256
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• 2010

Since biodiesel as bioenergy is defined as ester compounds formed by esterification of animal/vegetable oils, in this study three vegetable cooking oils (market, waste and refined waste ones) were esterified by reactions of alkali catalyst and immobilized enzyme. The fatty acid composition of the formed ester compounds was analyzed to investigate the feasibility of biodiesel production. By lipolysis (i.e, hydrolysis of Triglyceride (TG)), all three vegetable oils used in this study were found to produce Diglyceride (DG), Monoglyceride (MD) and Fatty acid ethylester (FAEE). However, the amount of produced FAEE (which can be used as an energy source) was in the increasing order of market cooking oil, waste one and refined waste one. With NaOH catalyst, FAEE was produced about 24.92, 17.63 and 11.31 % for the respective oils while adding Lipozyme TL produced FAEE about 43.54, 38.16 and 24.47 %, respectively. This indicates that enzyme catalyst is more effective than alkali one for transesterification. In addition, it was found that the composition of fatty acids produced by hydrolysis of TG was unchanged with alkali and immobilized enzyme reactions. Thus it can be expected that stable conditions remain in the course of mixing with gasoline whose composition is similar to that of the fatty acids.

• 한국자기공명학회논문지
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• 제5권1호
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• pp.19-28
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• 2001

Miscibility and morphology in blends of bisphenol-A type polycarbonate and poly (ester-ether) elastomer with different compositions are studied by solid-state NMR spectroscopy. $^{13}$ C Solid-state NMR of CP/MAS/TOSS/DD, CP/MAS/DD, inversion recovery CP/MAS/DD, and 2D rotor driven spin diffusion techniques are used to identify the miscibility, morphology, and transesterification in blends. The blends of PC /BT elastomer with 15% to 42% of soft segment seem to be single phase miscible mixing and those of PC/PBT and PC/PBT elastomer with 62% of soft segment are cocontinuous two phase immiscible mixing. No significant transesterification reactions are observed in blends with different compositions.