• Title/Summary/Keyword: phosgene

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Reaction Kinetics for the Synthesis of Diphenyl Carbonate from Dimethyl Carbonate (디메틸 카보네이트(DMC)로부터 디페닐카보네이트(DPC) 합성을 위한 반응속도론)

  • Choi, Yu-Mi;Cho, Im-Pyo;Cho, Hoon;Lee, Jin-Hong;Han, Myung-Wan
    • Korean Chemical Engineering Research
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    • v.50 no.5
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    • pp.766-771
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    • 2012
  • PC (polycarbonate) is one of the widely used engineering plastics. Polycarbonate (PC) is traditionally produced by the reaction of phosgene and bisphenol-A. This phosgene process has the disadvantage as the high toxicity and corrosiveness of phosgene. The main point of focus to overcome the disadvantage of phosgene based process has been a route through dimethyl carbonate (DMC) to diphenyl carbonate (DPC). In this paper, for the DPC synthesis reaction using PBO as a catalyst, the effect of reaction temperature, reactant ratio, catalyst concentration on the reaction yield was investigated. A kinetic model for the DPC synthesis reaction was proposed and kinetic parameters for the proposed model was determined from batch reactor experiments. The predicted results by the proposed model were in good agreement with the experimental results.

Kinetics and Mechanism of Hydrolysis of Benzenesulfonylimido Phosgene (Benzenesulfonylimido Phosgene 의 加水分解 反鷹메카니즘과 反鷹速度論的 硏究)

  • Sung, Nack-Do;Han, Sun-Ho;Kwon, Ki-Sung;Kim, Tae-Rin
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.259-264
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    • 1984
  • The rate constants for the hydrolysis of benzenesulfonylimido phosgene at various pH were determined by ultraviolet spectrophotometry in 1 : 4 dioxane-water mixed solvents at 25$^{\circ}$C and a rate equation which can be applied over a wide pH range was obtained. Based on the Grunwald-Winstein equation, m = 0.4 was obtained. The thermodynamic activation parameters for the hydrolysis were ${\Delta}H^{\neq}$ = 15kcal mol$^{-1}$, ${\Delta}S^{\neq}$ = 21e.u. at pH 4.0 and $ {\Delta}H^{\neq}$ = 8kcal. mol$^{-1}$, ${\Delta}S^{\neq}$ = -39e.u. at pH 11.0, respectively. It was concluded that the hydrolysis of benzenesulfonylimido phosgene in 1 : 4 dioxane-water mixed solvents proceed via nucleophilic addition-elimination.

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Chlorination of Alcohols Using Potassium Carbonate and Silicon Tetrachloride (탄산칼륨 존재하에서 사염화규소를 이용한 알코올의 염소화반응)

  • Ha, Dong Soo;Kim, Hyeung Ae
    • Journal of the Korean Chemical Society
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    • v.41 no.10
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    • pp.535-540
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    • 1997
  • Potassium carbonate reacts with silicon tetrachloride to form trichlorosilyloxy carbonylchloride which reacts subsequently with another molecule of silicon tetrachloride leading to phosgene eventually in chlorinated solvents. This in situ generated trichlorosilyloxy carbonylchloride or phosgene were found to be very effective for the chlorination of a wide variety of alcohols to the corresponding chlorides. Primary, secondary and benzylic alcohols were converted into corresponding chlorides when treated with silicon tetrachloride in the presence of potassium carbonate at room temperature.

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A Study on the Chemical Warfare Agents Dispersion Modelling in a Naturally Ventilated Indoor System (자연환기상태 실내공간에서의 화학작용제 확산 모델링 연구)

  • Kye, Young-Sik;Chung, Woo-Young;Kim, Yong-Joon
    • Journal of the Korea Institute of Military Science and Technology
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    • v.11 no.4
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    • pp.133-140
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    • 2008
  • The purpose of this study is to provide response methods to minimize the damage from chemical terrorism in a naturally ventilated indoor system using several types of dispersion simulations. Three chemical warfare agents such as sarin(GB), phosgene and chlorine gas which have high potential to be used in terror or to be involved with accidents were selected in this simulation. Fire dynamic simulation based on Large Eddy Simulation which is effective because of less computational effort and detailed expression of the dispersion flow was adopted to describe the dispersion behavior of these agents. When the vent speed is 0.005m/s, the heights of 0.1 agent mass fraction are 0.9m for sarin, 1.0m for phosgene and 1.1m for chlorine gas, and the maximum mass fraction are 0.27 for all three agents. However, when the vent speed is increased to 0.05m/s, the heights of 0.1 agent mass fraction become 1.6m for all three agents and maximum mass fraction inside the room increase to 0.70 for sarin, 0.58 for phosgene and 0.53 for chlorine gas. It is shown that molecular weight of the agents has an important role for dispersion, and it is important to install ventilation system with height less than 1.6m to minimize the damage from chemical toxicity.

Improvement of the Synthetic Route for Epinastine Antihistamine (에피나스틴 항히스타민제의 합성법 개선)

  • Baek, Du-Jong;Kim, Moon-Sik
    • Journal of the Korean Chemical Society
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    • v.54 no.4
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    • pp.447-450
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    • 2010
  • In this study, the improved large-scale synthetic route for epinastine hydrochloride, the second-generation antihistamine, was developed. The original synthetic route involves the synthesis of an aminomethyl derivative, the main intermediate, and in this process hazardous materials such as very toxic phosgene and sodium cyanide along with the explosive and expensive aluminum chloride and lithium aluminum hydride were used. In order to improve the synthetic route, we developed industrially very useful process to prepare the aminomethyl intermediate by the synthesis of the phthalimidomethyl derivative first and easy removal of the phthalyl group using hydrochloric acid or methyl hydrazine, and hazardous materials and expensive reagents were excluded in this process.

The Simulation and Control of the Reactive Distillation Process for Dimethylcarbonate(DMC) Production

  • Jang, Yong-Hee;Yang, Dae-Ryook
    • 제어로봇시스템학회:학술대회논문집
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    • 2004.08a
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    • pp.1215-1220
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    • 2004
  • Reactive distillation (RD) is a combination process where both separation and reaction are considered simultaneously in a single vessel. This kind of combination to enhance the overall performance is not a new attempt in the chemical engineering areas. The recovery of ammonia in the classic Solvay process for soda ash of the 1860s may be cited as probably the first commercial application of RD. The RD system has been used for a long time as a useful process and recently the importance of the RD is enlarged more and more. In addition to that, the application fields of RD are diversely diverged. To make the most of the characteristic of RD system, we must decide the best operating condition under which the process shows the most effective productivity and should decide the best control algorithm which satisfies an optimal operating condition. Phosgene which is a highly reactive chemical is used for the production of isocyanates and polycarbonates. Because it has high reactivity and toxicity, its utilization is increasingly burdened by growing safety measures to be adopted during its production. Dimethyl Carbonate (DMC) was proposed as a substitute of phosgene because it is non-toxic and environmentally benign chemical. In this study, RD is used for DMC production process and the transesterification is performed inside of column to produce DMC. In transesterification, the methanol and ethylene carbonate (EC) are used as the reactants. This process use homogeneous catalyst and the azeotrope exists between the reactant and product. Owing to azeotrope, we should use two distillation columns. For this DMC production process, we can suggest two configurations. One is EC excess process and the other is methanol excess process. From the comparison of steady state simulation results where the Naphtali-Sandholm algorithm is used, it showed the better performance to use the methanol excess process configuration than EC excess process. Then, the dynamic simulation was performed to be based on the steady state simulation results and the optimal control system was designed. In addition to that, the optimal operating condition was suggested from previous results.

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Study on the analytical method using GC-MS for the accident preparedness substances (실험실 GC-MS를 이용한 사고대비물질 분석방법 연구)

  • Kim, Kijoon;Lee, Jinseon;Lee, Suyeong;Hwang, Seungryul;Kim, Younghee;Seok, Gwangseol
    • Analytical Science and Technology
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    • v.26 no.1
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    • pp.80-85
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    • 2013
  • The sixty nine accident preparedness substances (APS) having high probability of chemical accident are controlled under the Toxic Chemicals Control Act (TCCA). Around the world, there has been a growing interest in the analysis of chemical warfare agent (CWAs). When a chemical accident occurs, it is generally required to detect and identify APS. However, the quantitative analytical data remain limited in Korea. In this study, an analytical method using GC/MS for volatile organic chemicals was established and a quantitative analysis method was studied. The calibration curve for 25 chemicals were obtained and 21 chemicals showed higher coefficient of determination ($r^2$ >0.998).