Pentachloroethane의 불소화 반응에 관한 연구

박건유; 권영수; 김훈식; 이상득; 이병권

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.2, 318-323, June, 1993

Export Citation

Pentachloroethane의 불소화 반응에 관한 연구

A Study on the Fluorination of Pentachloroethane

박건유, 권영수, 김훈식, 이상득, 이병권

초록

CFC-11(CFCl₃)의 대체품인 HCFC-123(CF₃CHCl₂)의 합성을 위하여 Pentachloroethane(CHCl_2,CCl₃)을 제조하고, 이것을 antimony pentahalide 촉매의 존재하에서 불화수소와 반응시켰다. CHCI₂CCl₃의 불소화 반응은 촉매와 반응물간의 Cl-F교환 mechanism에 의해 진행되었으며 CHCl_2,CCl₃의 불화도는 반응온도가 높을수록 증가하는 경향을 보여 주었다. 촉매농도 또한 생성물의 불화도에 영향을 미치나 반응온도에 비해 상대적으로 낮았다. CC1₃CFCl₂, CFCl₂, CF₂ClCFCl₂와 같은 부산물의 생성원인을 규명하기 위한 실험을 실시하여 부산물 생성 mechanism을 제안하였다.

Pentachloroethane(CHCl₂CC1₃) was synthesized and reacted with hydrogen fluoride using antimony pentahalide catalyst(SbCl_xF_y) in order to manufacture HCFC-123(CF₃CHCl₂), a potential CFC-11(CFC1₃) substitute candidate. Products analyses showed the fluorination proceeds through fluorine-chlorine exchanges between HF/SbCl_xF_y and SbCl_xF_y/CC1₃CHCl₂ respectively. The degree of fluorination of CCl₃ group in pentachloroethane was greatly affected on the reaction temperature, but the effect of catalyst concentration was relatively small. Mechanistic study was also performed to elucidate the pathway to the formation of side-products such as CCl₃CFCl₂, CFCl₂CFCl₂ and CF₂ClCFCl₂.

[References]

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duPont EI, U.S. Patent, 2,410,358 (1946)

[1] UNEP, "Montreal Protocol on Substances that Deplete the Ozone Layer," Final Act. (1987)

[2] Nelson P, Wevill SL, "Alternative Formulations and Packaging to Reduce Use of Chlorofluorocarbons," Noyes Data Corporation, New Jersey (1990)

[3] 이윤용, "CRC 대체물질 개발 현황과 전망," 오존층파괴물질 사용 합리화를 위한 세미나, 한국정밀화학공업진흥회 (1992)

[4] 상공부, "오존층 보호를 위한 특정물질의 제조규제 등에 관한 법률," (1991)

[5] Fischer DA, "Ozone Depletion Potential," in "Scinentific Assesment of Stratospheric Ozone," WMO Global Ozone Research and Monitoring Project-Report. No. 20 (1989)

[6] Lovelace AM, "Aliphatic Fluorine Compounds," Reinhold Publ. Corp., New York (1958)

[7] Stacey M, Adv. Fluor. Chem., 3, 129 (1963)

[8] Sheppard WA, Sharts CM, "Organic Fluorine Chemistry," 77, Benjamin, New York (1969)

[9] Santacesaria E, Serio MD, J. Fluor. Chem., 44, 87 (1989)

[10] Feiring AE, J. Fluor. Chem., 13, 7 (1979)

[11] duPont EI, U.S. Patent, 4,766,260 (1988)

[12] duPont EI, U.S. Patent, 4,847,181 (1989)

[13] Toa Gosei Chemical Industry Co., Ltd., France Patent, 2,057,604 (1972)

[14] Kolditz L, Lieth W, Z. Anorg. Chem., 310, 236 (1969)

[15] Preiss H, Z. Chem., 6, 350 (1966)

[16] Birchall T, J. Chem. Soc.-Dalton Trans., 1469 (1977)

[17] Muetterties EL, Inorg. Chem., 3, 1298 (1964)

[18] Glajch JL, Schindel WG, LC-GC, 4, 574 (1986)

[19] Hudlicky M, "Chemistry of Organic Fluorine Compounds," 100, Ellis Horwood Ltd., New York (1976)

[20] duPont EI, U.S. Patent, 2,410,358 (1946)