• Title/Summary/Keyword: Alcoholysis

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폴리에틸렌테레프탈레이트/폴리카프로락톤 용융 블렌드에서 폴리카프로락톤 분자량 고 촉매 함량에 따른 에스테르 교환 반응 거동

  • 임경율;윤기종
    • Proceedings of the Korean Fiber Society Conference
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    • 1998.10a
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    • pp.5-8
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    • 1998
  • 폴리에스테르 공중합체의 합성에 이용될 수 있는 에스테르 교환 반응은 alcoholysis, acidolysis 및 transesterification 반응들에 의해 복합적으로 진행되며 이 때 각각의 반응 속도를 비교하여 보면 어느 한 쪽 분자쇄의 말단 알코올기가 다른 쪽 분자쇄의 에스테르기를 공격하는 alcoholysis 반응이 가장 빠르고 카르복실기가 에스테르를 공격하는 acidolysis 및 두 고분자 주쇄의 에스테르기 상호간에 발생하는 transesterification 반응들은 alcoholysis 반응에 비해 느린 것으로 알려져 있다. (중략)

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The Effects of Blend Composition and Blending Time on the Ester Interchange Reaction and Tensile Properties of PLA/LPCL/HPCL Blends

  • Yoon, Cheol-Soo;Ji, Dong-Sun
    • Fibers and Polymers
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    • v.4 no.2
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    • pp.59-65
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    • 2003
  • PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly($\varepsilon$-caprolactone) (LPCL), and high molecular weight poly($\varepsilon$-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable fila-ment sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by $^1{H-NMR}$, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreafed by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at $200^{\circ}C$ for 30-60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three poly-mers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.

InCl3-Catalyzed Regioselective Ring-Opening Reactions of Epoxides to β-Hydroxy Ethers

  • Kim, Byeong-Hyo;Piao, Fengyu;Lee, Eun-Joo;Kim, Ji-Sook;Jun, Young-Moo;Lee, Byung-Min
    • Bulletin of the Korean Chemical Society
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    • v.25 no.6
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    • pp.881-888
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    • 2004
  • By applying a catalytic amount of indium trichloride, regioselective ring-opening of epoxides to ${\beta}$-hydroxy ethers was established. While the alcoholysis of styrene oxides produed $S_N1$-type product, the alcoholysis of ${\alpha}$-heteroatom-substituted epoxides predominantly produced $S_N2$-type product.

Synthesis of Histamine $H_2$-receptor antagonists - Synthesis of 5,6-dihydro[2,1-b]thiazole derivatives - (Histamine $H_2$-수용체길항제의 합성 - 5,6-Dihydroimidazo[2,1-b]thiazole 유도체의 합성 -)

  • 박상우;이강노
    • YAKHAK HOEJI
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    • v.35 no.5
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    • pp.368-371
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    • 1991
  • For the development of new antiulcer agents 5, 6-dihydroimidazo[2, 1-b]- thiazoles substituted at the 3-position are sythesized. Thus, the reaction of 3-chloromethyl-5, 6-dihydroimidazo[2, 1-b]thiazole(2) with thiourea and subsequently with 3-chloro-propionitrile gives 3-[3-[5, 6-dihydroimidazo[2, 1-b]thiazolyl]methylthio]propionitrile(4), which by partial alcoholysis with methanol is converted into methyl-3-[3-[5, 6-dihydro-imidazo[2, 1-b]thiazoyl]methylthio]propionimidate(5) . This compound(5) is treated finally with sulfamide or sulfonamides. 3-[3-[5, 6-dihydroimidazo[2, 1-b]thiazoyl]methylthiol-N$^{2}$-sulfamoyl-propionamidine(6) inhibited gastric acid secretion (45%) when administered intraduodenally (100 mg/kg) to pylorus-ligated rats.

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Synthesis and Characterization of New Polyaza Macrocyclic Nickel(Ⅱ) and Copper(Ⅱ) Complexes Two Nitrile or Imidate Ester Pendant Arms: Metal-Mediated Hydrolysis and Alcoholysis of the Nitrile Groups

  • Kang, Shin-Geol;Song, Jeong-Hoon;Jeong, Jong-Hwa
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.824-829
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    • 2002
  • New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.

Preparation of Silica Nanoparticles via Two-Step Process Utilizing Mixed Chlorosilane Residues

  • Su, Yonghong;Xu, Bugang;Cai, Jixiang;Chen, Liang;Huang, Bing
    • Journal of the Korean Ceramic Society
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    • v.55 no.6
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    • pp.562-569
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    • 2018
  • We propose an economic and facile method for the preparation of silica nanoparticles through a two-step process utilizing chlorosilane residues. Mixed chlorosilane residue was alcoholized with absolute ethanol as a first step to form tetraethoxysilane (TEOS). The TEOS was then utilized as a silicon source to synthesize silica nanoparticles in a sol-gel method. The alcoholysis process was designed and optimized utilizing the Taguchi experimental design method and the yield of TEOS was as high as 82.2% under optimal synthetic conditions. Similarly, the Taguchi method was also utilized to study the effects of synthesis factors on the particle size of silica nanoparticles. The results of statistical analysis indicate that the concentration of ammonia has a greater influence on particle size compared to the mass fractions of TEOS and polyethylene glycol (4.6% and 9.7%). The purity of the silica particles synthesized in our experiments is high, but the specific surface area and pore volume are small.

Transition-State Structures for Solvolysis of Methanesulfonyl Chloride

  • 양기열;강금덕;구인선;이익준
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1186-1191
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    • 1997
  • Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

Stability of Oil-in-Water Emulsions with Different Saturation Degrees from Beef Tallow Alcoholysis Products (우지 Alcoholysis 반응물을 이용한 Oil-in-Water Emulsion의 포화도에 따른 산화특성 및 안정성 연구)

  • Zhang, Hua;Lee, Young-Hwa;Shin, Jung-Ah;Lee, Ki-Teak;Hong, Soon-Teak
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.42 no.6
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    • pp.933-940
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    • 2013
  • In this study, methyl esters with different saturated fatty acids (SFA) were prepared by urea fractionation to make an oil-in-water emulsion. Emulsion characteristics (emulsion stability and oxidative stability) of the methyl ester emulsion were then studied at different percentages of methyl ester saturation (5, 28, 39, 50, and 72%, termed ${\Sigma}$SFA5, ${\Sigma}$SFA28, ${\Sigma}$SFA39, ${\Sigma}$SFA50, and ${\Sigma}$SFA72, respectively). The stability of emulsions (ES) with different SFA content was 46.0 (${\Sigma}$SFA5), 39.5 (${\Sigma}$SFA28), 32.7 (${\Sigma}$SFA39), 32.6 (${\Sigma}$SFA50), and 27.3 (${\Sigma}$SFA72). Results from Turbiscan showed that creaming or clarification, based on the backscattering intensity, was more pronounced with increases in the saturation degree of the emulsion. These results implied that the emulsions with lower saturation were more stable. During 30 days of storage, the lipid peroxide value increased for all emulsions, with the increase less pronounced with the increasing saturation of the emulsion; 1.880 (${\Sigma}$ SFA5), 1.267 (${\Sigma}$SFA28), 1.062 (${\Sigma}$SFA39), 0.342 (${\Sigma}$SFA50) and 0.153 (${\Sigma}$SFA72) mg $H_2O_2/mL$ emulsion. In addition, thiobarbituric acid reactive substances (TBARS) values were significantly lower in emulsions with high saturation (4.419 mg for ${\Sigma}$SFA50 and 4.226 mg for ${\Sigma}$SFA72) than emulsions with low saturation (6.229 mg for ${\Sigma}$SFA5, 6.801 mg for ${\Sigma}$SFA28 and 6.246 mg for ${\Sigma}$SFA39). In conclusion, the emulsions with a higher saturation degree of methyl esters showed lower emulsion stability but better oxidation stability.