상이동 촉매에 의한 Glycidyl Vinyl Ether와 이산화탄소의 부가반응

문정열; 양정규; 박대원; 이미혜; 이진국

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.6, 1162-1169, December, 1995

Export Citation

상이동 촉매에 의한 Glycidyl Vinyl Ether와 이산화탄소의 부가반응

Addition Reaction of Glycidyl Vinyl Ether with Carbon Dioxide Using Phase Transfer Catalysts

문정열, 양정규, 박대원, 이미혜, 이진국

초록

본 연구는 이산화탄소와 glycidyl vinyl ether(GVE)의 부가반응에 대하여 상이동 촉매의 특성을 고찰한 것이다. 4급 암모늄염 상이동 촉매의 경우 상압에서도 비교적 좋은 GVE 전화율을 나타내었고, 알킬기의 크기가 크고 짝음 이온의 친수성이 강할수록 촉매활성이 높았다. 폴리에틸렌글리콜이나 triethylamine을 NaI와 함께 사용한 결과 NaI보다 (2-oxo-1,3-dioxolane-4-yl)methyl vinyl ether(OVE)의 수율이 높았다. 그러나 크라운 에테르는 촉매활성을 감소시켰다. 한편 속도론적 고찰결과 반응속도는 GVE의 농도에 대하여 유사 1차 반응으로 나타났으며, 상이동 촉매의 역할이 포함된 반응메카니즘도 함께 제시하였다.

This study is related to the investigation of the characteristics of phase transfer catalysts on the addition reaction of carbon dioxide and glycidyl vinyl ether(GVE). Among the quaternary ammonium salts tested, the ones with the higher alkyl chain length and with the more hydrophilic counter anion showed higher catalytic activity. Mixed catalysts of(polyethylene glycols + NaI) and (triethylamine + NaI) showed higher yield of (2-oxo-1,3-dioxolane-4-yl)methyl vinyl ether(OVE) than NaI itself, but the catalyst activity decreased by addition of a crown ether. Kinetic studies showed that the reaction rate was pseudo-first order with respect to the concentration of GVE. A mechanism of the reaction involving the role of phase transfer catalysts was also proposed.

[References]

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Rokicki G, Jezewski P, Polym. J., 20, 409 (1988)
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Kihara N, Endo T, J. Chem. Soc.-Chem. Commun., 937 (1994)
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Starks CM, Liotta CL, Halpern M, "Phase Transfer Catalysis," Chapman & Hall, N.Y. (1994)
Kihara N, Hara N, Endo T, J. Org. Chem., 58, 6198 (1993)
Sasson Y, Zahalka HA, Can. J. Chem., 67, 245 (1989)
Schultz RA, Dishong DM, Gokel GW, J. Am. Chem. Soc., 104, 625 (1982)
Yamashita J, Kameyama A, Nishiknbo T, Fukuda W, Tomoi M, Kobunshi Ronbunshu, 50, 577 (1993)
Hwu DH, Hwang C, Yeh MY, Jung HM, Shih YP, Ind. Eng. Chem. Res., 29, 2214 (1990)

[1] Choi MJ, Lee KW, Catalysis, 11, 77 (1995)

[2] Rokicki G, Powlicki J, Kuran W, Polym. J., 17, 509 (1985)

[3] Rokicki G, Jezewski P, Polym. J., 20, 409 (1988)

[4] Rokicki G, Kuran W, Marcinak BP, Monat. Chem., 115, 205 (1984)

[5] Kihara N, Endo T, J. Chem. Soc.-Chem. Commun., 937 (1994)

[6] Kihara N, Endo T, Makromol. Chem., 193, 1481 (1992)

[7] Nishikubo T, Kameyama A, Sasano M, J. Polym. Sci. A: Polym. Chem., 32(2), 301 (1994)

[8] Katz HE, Macromolecules, 20, 2026 (1987)

[9] Starks CM, Liotta CL, Halpern M, "Phase Transfer Catalysis," Chapman & Hall, N.Y. (1994)

[10] Kihara N, Hara N, Endo T, J. Org. Chem., 58, 6198 (1993)

[11] Sasson Y, Zahalka HA, Can. J. Chem., 67, 245 (1989)

[12] Schultz RA, Dishong DM, Gokel GW, J. Am. Chem. Soc., 104, 625 (1982)

[13] Yamashita J, Kameyama A, Nishiknbo T, Fukuda W, Tomoi M, Kobunshi Ronbunshu, 50, 577 (1993)

[14] Hwu DH, Hwang C, Yeh MY, Jung HM, Shih YP, Ind. Eng. Chem. Res., 29, 2214 (1990)