4차 암모늄염 촉매를 이용한 Poly(GMA)에의 이산화탄소 직접 고정화

성충기; 김경훈; 문정열; 천승우; 나석은; 박대원

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.1, 129-134, February, 1999

Export Citation

4차 암모늄염 촉매를 이용한 Poly(GMA)에의 이산화탄소 직접 고정화

Direct Incorporation of Carbon Dioxide to Poly(GMA) Using Quaternary Ammonium Salt Catalysts

성충기, 김경훈, 문정열, 천승우, 나석은, 박대원

초록

4차 암모늄염 촉매 존재하에서 poly(glycidyl methacrylate)[poly(GMA)]에 이산화탄소를 직접 부가시켜 poly[(1,3-dioxolane-2-oxo-4-yl)methyl methacrylate][poly(DOMA)]를 합성하였다. 4차 암모늄염 촉매는 높은 이산화탄소 고정화 효율을 나타내었으며, 양이온의 크기가 클수록, 짝음이온의 친핵성이 강할수록 높은 촉매 활성을 나타내었다. 또한 반응온도가 높을수록 높은 이산화탄소 부가율을 나타내었다. 한편 고압 회분 반응기에서 이산화탄소의 압력변화를 관찰함으로써 실시한 속도론적 고찰 결과 반응속도는 poly(GMA)와 이산화탄소의 농도에 대하여 각각 1차 반응이었고, 이때 반응속도상수 k는 0.69L/mol·h이었다. DMSO를 용매로 사용한 경우 80℃에서의 CO₂의 Henry 상수 H'는 6.8×10^-4 mol/L·KPa로 나타났다.

This study is related to the investigation of the direct incorporation of CO₂ to polymer using quaternary ammonium salt catalysts. Quaternary ammonium salts showed good catalytic activity of CO₂ fixation in the synthesis of poly[(1,3-dioxolane-2-oxo-4-yl)methyl methacrylate] [poly(DOMA)] by the direct incorporation of CO₂ to poly(glycidyl methacrylate)[poly(GMA)]. Among the salts tested, the ones with higher alkyl chain length and with more nucleophilic counter anion showed higher catalytic activity. The yield of carbon dioxide addition increased with the reaction temperature. Kinetic study was carried out by measuring the variation of CO₂, pressure in a high pressure batch reactor. The reaction rate was first order to the concentration of poly(GMA) and CO₂, respectively. The rate constant was 0.69 L/mol·h and Henry's constant of CO₂ in DMSO at 80℃ was 6.8×10^-4 mol/L·KPa.

Keywords:Carbon Dioxide;Direct Incorporation;Poly(GMA);Quaternary Ammonium Salt Catalysts

[References]

Ramanathan V, Cierone RJ, Singh HB, Kiehl JT, J. Geophys. Res., 90, 5547 (1985)
Choi MJ, Lee KW, Catalysis, 11, 77 (1995)
Rokicki G, Pawlicki J, Kuran W, Polym. J., 17, 509 (1985)
Rokicki G, Jezewski P, Polym. J., 20, 409 (1988)
Rokicki G, Kuran W, Marcinak BP, Monat. Chem., 115, 205 (1984)
Kihara N, Endo T, Makromol. Chem., 193, 1481 (1992)
Kihara N, Endo T, J. Chem. Soc.-Chem. Commun., 937 (1994)
Kihara N, Endo T, Makromol., 25, 4824 (1992)
Sakai T, Kihara N, Endo T, Makromol., 28, 4701 (1995)
Park DW, Moon JY, Yang JG, Jung SM, Lee JK, Ha CS, Stud. Surf. Sci. Catal., 114, 403 (1998)
Moon JY, Yang JG, Park DW, Lee JK, React. Kinet. Catal. Lett., 61, 315 (1997)
Starks CM, Liotta CL, Halpern M, "Phase Transfer Catalysis," Chapman & Hall, N.Y. (1994)
Yang JG, Moon JY, Jung SK, Park DW, Lee JK, J. Korean Ind. Eng. Chem., 7(6), 1156 (1996)
Perason RG, Songstad J, J. Org. Chem., 32, 2899 (1967)
Kihara N, Hara N, Endo T, J. Org. Chem., 58, 6198 (1993)
Park DW, Moon JY, Yang JG, Park SW, Lee JK, J. Korean Ind. Eng. Chem., 6(6), 1206 (1995)
Wilhelm E, Battino R, Wilcock RJ, Chem. Rev., 77, 219 (1977)

[Referenced By]

[1] Ramanathan V, Cierone RJ, Singh HB, Kiehl JT, J. Geophys. Res., 90, 5547 (1985)

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

[3] Rokicki G, Pawlicki J, Kuran W, Polym. J., 17, 509 (1985)

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

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

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

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

[8] Kihara N, Endo T, Makromol., 25, 4824 (1992)

[9] Sakai T, Kihara N, Endo T, Makromol., 28, 4701 (1995)

[10] Park DW, Moon JY, Yang JG, Jung SM, Lee JK, Ha CS, Stud. Surf. Sci. Catal., 114, 403 (1998)

[11] Moon JY, Yang JG, Park DW, Lee JK, React. Kinet. Catal. Lett., 61, 315 (1997)

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

[13] Yang JG, Moon JY, Jung SK, Park DW, Lee JK, J. Korean Ind. Eng. Chem., 7(6), 1156 (1996)

[14] Perason RG, Songstad J, J. Org. Chem., 32, 2899 (1967)

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

[16] Park DW, Moon JY, Yang JG, Park SW, Lee JK, J. Korean Ind. Eng. Chem., 6(6), 1206 (1995)

[17] Wilhelm E, Battino R, Wilcock RJ, Chem. Rev., 77, 219 (1977)