• Title/Summary/Keyword: methanolysis

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Recycling of Poly(ethylene terephthalate) via Methanolysis without Catalyst (무촉매 메탄올 분해에 의한 Poly(ethylene terephthalate)의 재활용에 관한 연구)

  • Lee, Yoon-Bae;shin, Jae-Sick
    • Clean Technology
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    • v.8 no.1
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    • pp.39-44
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    • 2002
  • In order to recycle poly(ethylene terephthalate), methanolysis has been investigated at elevated temperature and under high pressure without catalyst to afford dimethyl terephthalate and ethylene glycol. The reaction was carried out under 62 atm, $310^{\circ}C$ for 50min to obtain 98% dimethyl terephthalate. The method has been suggested as a simple and economical one to recycle the poly(ethylene terephthalate).

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Distinction between the Influence of Dielectric Constant and of Methanol Concentration on Trypsin-Catalyzed Hydrolysis and Methanolysis

  • Park, Hyun;Chi, Young-Min
    • Journal of Microbiology and Biotechnology
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    • v.8 no.6
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    • pp.656-662
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    • 1998
  • To make a distinction between the influence of the dielectric constant and of methanol concentration on trypsin-catalyzed hydrolysis and methanolysis at $0^{\circ}C$, a model reaction of $N^u$-benzyloxycarbonyl-L-lysine p-nitrophenyl ester with water-methanol mixtures was chosen and a kinetic study done. The $k_{cat}$ values increased with methanol concentration, in a linear manner whereas $K_{M}$ values increased in a log-linear fashion. However, the $k_{cat},$_{M}$ ratio increased at lower methanol concentrations than 30% and then began to decrease at higher concentrations. The decrease in $k_{catK_M}$observed at higher than 30% methanol concentrations is attributed to the hydrophobic partitioning effect on substrate binding. On the other hand, the increase in $k_{catK_M}$ in the 0~30% methanol concentration range seems to be due to the effect of nucleophilic cosolvent on $k_{cat}$ and of the dielectric constant on $k_m$. This explanation was verified by measuring the effect of varying the dielectric constant of the medium on kinetic constants with isopropyl alcohol chemically unrelated to the enzyme reaction as the methanol concentration is maintained at a constant level. Therefore, we conclude that the effect of increasing the methanol concentration in the model reaction on the kinetic parameters $k_{cat \;and\;{K_M}}$ is caused by changes in both the nucleophilicity and the dielectric constant of the medium. Based on product analysis, the increase in $k_4, k_3$by decreasing the temperature can be accounted for by the suppression of hydrolytic reactions. This observation indicates that the nucleophile is favored by low temperatures. There was no loss of trypsin activity over a 10 h period in 60% methanol concentration at $pH^*\; 5.5,\; 0^{\circ}C$.EX>.

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Kinetics of the KOH Catalyzed-Methanolysis for Biodiesel Production from Fat of Tra Catfish

  • Huong, Le Thi Thanh;Tan, Phan Minh;Hoa, Tran Thi Viet;Lee, Soo
    • Journal of the Korean Applied Science and Technology
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    • v.25 no.4
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    • pp.418-428
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    • 2008
  • Transesterification of fat of Tra catfish with methanol in the presence of the KOH catalyst yields fatty acid methyl esters (FAME) and glycerol (GL). The effects of the reaction temperature and reaction time on rate constants and kinetic order were investigated. Three regions were observed. In the initial stage, the immiscibility of the Tra fat and methanol limited the reaction rate, hence this region was controlled by the mass transfer. Subsequent to this region, produced FAME like a co-solvent made the reaction mixture homogeneous, therefore the conversion rate increased rapidly so it was controlled by the kinetic parameters of the reaction until the equilibrium was approached in the final slow region. A second-order kinetic mechanism was proposed involving second regions for the forward reaction. The rate determining step for the overall KOH catalyzed-methanolysis of Tra fat was the conversion of triglycerides (TG) to diglycerides (DG). This rate constant was increased from 0.003 to $0.019min^{-1}$ when the reaction temperature was increased from 35 to $60^{\circ}C$. Its calculated activation energy was 14.379 ($kcal.mol^{-1}$).

Solvolysis of Phenylacetyl Chlorides in Methanol-Acetonitrile Mixtures

  • Lee Ikchoon;Huh Chul;Lee Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.10 no.1
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    • pp.47-50
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    • 1989
  • The methanolysis reactions of phenylacetyl chlorides have been investigated in methanol-acetonitrile mixtures at temperatures ranging - $15.0-0.0^{\circ}C.$ Substituent and solvent effects on the rate supported an associative $S_N2$ mechanism for the solvolysis. Activation parameters indicated that the reaction is entropy controlled, while the a/s ratios of the Taft's solvactochromic correlation proved to be remarkably constant with a typical value of 0.50 that is consistent for the reactions proceeding by a typical $S_N2$ path.

Copolymerization of N-Vinylurea and Vinyl Acetate (Ⅱ). Solvent Effects in Radical Copolymerization (N-비닐尿素와 醋酸비닐의 混成重合 (第2報). 라디칼混成重合에서의 溶媒效果)

  • Woo Sik Kim;Hak-ki Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.80-85
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    • 1980
  • The free radical copolymeriaztion of N-vinylurea(VU) with vinyl acetate (VAc) was carried out at $60^{\circ}C$ in three solvents. VU-vinyl alcohol(VA) copolymers were prepared by the methanolysis of the VU-VAc copolymers. From the nitrogen content measurements of VU-VA copolymers, the monomer reactivity ratios for the VU-VAc copolymerization and the values of Alfrey-Price's Q and e for VU were determined. These Q and $\varrho$ values obtained in the cases of using methanol and methanol-dioxane as the polymerization solvents are comparable with those found for other monomers which have > NCO-pendent groups. The $\varrho$ value indicates that the urea group of VU is a electron-donating group. The copolymerization parameter of VU shows a strong effect of the solvents. These results are interpreted to be that VU is in equilibrium with its tautomer at the polymerization temperature.

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Cooperative Effects of Solvatochromic Parameters on the Ionizations of tert-Butyl Halides in MeOH-1,1,2,2-Tetrachloroethane Mixtures (MeOH-1,1,2,2-Tetrachloroethane 혼합용매에서 tert-Butyl Halides의 이온화에 미치는 분광용매화변수들의 협동효과)

  • Yeol Sakong;Shi Choon KIm;Jae Bum Choo
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.265-272
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    • 1986
  • Kinetic studies for the methanolysis of tert-butyl halides (t-BuCl, t-BuBr, t-BuI) were carried out in MeOH-1,1,2,2-tetrachloroethane mixtures. The solvatochromic comparison method was used with six indicators to analyze solvent effects on the ionizations of tert-butyl halides. It was shown that the cooperative effect of solvent polarity-polarizability was the most important factor influenced on the methanolysis rates of tert-butyl halides, but the electrophilic assistance for halide leaving group and the nucleophilic assistance for tert-butylium ion were considerably influential, too. And it was found that the electrophilic assistance caused by hydrogen bonding and the nucleophilic assistance for carbon center were stronger for more basic leaving group ($I^-) and more polarizable leaving group(t-BuCl

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Selective Enrichment of EPA end DHA by Adduct Formation of Folly Acids of Fish Oil and Urea (어유 지방산과 요소의 부가화합물 형성을 이용한 EPA와 DHA의 선택적 농축방법)

  • Han, Dae-Seok;Ahn, Byung-Hak;Shin, Hyun-Kyung
    • Korean Journal of Food Science and Technology
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    • v.22 no.5
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    • pp.520-525
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    • 1990
  • A modified method of urea adduct formation, in which water and organic solvent were used as the wetting agent and the reaction medium. respectively, is suggested to obviate methanolysis and to ease recovery in the separation of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) from fish oil. With the new method the fraction in which the total content of EPA. DHA and their precursors is more than 80% could be obtained. Although the total content of precursors in the concentrate was hardly affected by the kind of the wetting agent or the organic solvent, the content of EPA and DHA varied significantly depending on the organic solvent. This finding made it possible to selectively enrich the desired components. After DHA-enriched fraction (I)HA is 50%) was obtained by using pentane, EPA-enriched fraction ( EPA is 53%)) could be obtained from the residue of DHA-enriched fraction by using heptane.

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Study of Solvent Effects on the Ionization of tert-butyl Halide in MeOH-DMSO Mixtures (MeOH-DMSO 혼합용매중에서 tert-butyl halide의 이온화에 미치는 용매효과)

  • Yeol Sakong;Shi Choon Kim;Jin Sung Kim;Bon Su Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.1
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    • pp.45-51
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    • 1985
  • Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

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Partial Structure of Panax Saponin C (Panax Saponin C의 부분화학 구조)

  • Han, Byung-Hoon;Han, Yong-Nam
    • Korean Journal of Pharmacognosy
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    • v.3 no.4
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    • pp.211-213
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    • 1972
  • 전보에서 저자들은 인삼의 anti-inflammatory activity를 추적하여 Panax saponin A 및 C 로 명명된 dammalene계 glycoside를 분리하였고 A에 대해서는 이미 그 화학구조를 밝혀 보고한바 있다. 본보에서는 Panax saponin C(PS-C)의 부분 화학구조를 밝혀 보고코자 한다. PS-C는 산분해하면 panaxatriol 1 mol, glucose 2 mol 및 rhamnose 1 mol을 생성하고, acetylation하면 dodeca-acetate를 형성한다. 따라서 protopanaxtriol의 20[s]-수산기는 glycoside 결합에 참여하고있다. PS-C는 6 mol의 $HIO_4$를 소모하고 permethylate에 대한 methanolysis product를 GLC로 분석한 결과 2, 3, 4-trimethoxy-methyl-rhamnoside 1 mol과 $2,\;3,\;4,\;6-tetramethoxy-{\alpha}-methyl\;glucosied\;2\;mol$이 생성되므로 PS-C 중에 존재하는 3 mol의 sugar는 oligoside 결합에 의하지 않고 monoside결합에 의하여 연결되어 있고 glucose는 ${\beta}-glycoside$ 결합을 하고 있음을 의미한다.

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