Tetrabutylammonium Chloride 상이동 촉매에 의한 Methyl Methacrylate의 라디칼 중합

박상욱; 문진복; 하유수; 임균택

Polymer(Korea), Vol.17, No.1, 100-107, January, 1993

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Tetrabutylammonium Chloride 상이동 촉매에 의한 Methyl Methacrylate의 라디칼 중합

Radical Polymerization of Methyl Methacrylate with Phase Transfer Catalyst, Tetrabutylammonium Chloride

박상욱, 문진복, 하유수, 임균택

초록

Na₂S₂O₄ 수용액과 CCl₄-toluene 용액의 2상에서 수용액상에 용해하는 tetrabutylammonium chloride 상이동 촉매를 사용하여 methyl methacrylate의 라디칼 중합속도를 측정하여, 액-액 불균일계 접촉계면을 통한 라디칼 중합반응기구를 해석하였다. MMA의 중합속도는 수용액상에 존재하는 Q⁺ 이온의 농도와 S₂O₄^-2이온의 농도의 제곱근에 정비례하고 CCl₄와 MMA의 농도에 각각 정비례하였다.

The phase-transfer polymerization of methyl methacrylate with tetrabutylammonium chloride-Na₂S₂O₄-CCl₄ initiator system was investigated in an aqueous-organic two-phase system. The observed rates of polymerization were compared with those obtained from the polymerization mechanism proposed with a cyclic phase-transfer initiation step. The rate of polymerization was found to be proportional to the concentration of Q⁺ and square root of S₂O₄ in the aqueous solution and the feed quantity of CCl₄ and MMA.

[References]

Webewr WP, Gokel GW, "Phase Transfer Catalysis in Organic Synthesis," Springer-Verlag, New York (1977)
Starks CM, Liotta C, "Phase Transfer Catalysis-Principle and Techniques," Academic Press, New York (1978)
Dehmlow EV, Dehmlow SS, "Phase Transfer Catalysis," Verlag Chemie, 2nd ed., Weinheim (1983)
Starks CM, "Phase-Transfer Catalysis, New Chemistry, Catalysis, and Applications," Am. Chem Soc., Washington, D.C. (1987)
Imai Y, Abe S, Ueda M, J. Polym. Sci. A: Polym. Chem., 19, 3285 (1981)
Podkoscielny W, Kultys A, J. Appl. Polym. Sci., 26, 1143 (1981)
Yamazaki N, Imai Y, Polym. J., 15, 603 (1983)
Tsai H, Lee Y, J. Polym. Sci. A: Polym. Chem., 25, 1505 (1987)
Kellman R, Willians RF, Dimotsis G, Gerbi DJ, Willians JC, J. Am. Chem. Soc., 109, 128 (1987)
Yamada B, Yasuda Y, Matsudita T, Otsu T, J. Polym. Sci. C: Polym. Lett., 14, 277 (1976)
Reetz MT, Ostarek R, J. Chem. Soc.-Chem. Commun., 213 (1988)
Rasmussen JK, Smith HK, J. Am. Chem. Soc., 103, 730 (1981)
Jayakrishnan A, Shah DO, J. Polym. Sci. A: Polym. Chem., 21, 3201 (1983)
Jayakrishnan A, Shah DO, J. Appl. Polym. Sci., 29, 2937 (1984)
Rasmussen JK, Heilmann SM, Krepski LR, Smith HK, J. Am. Chem. Soc., 109, 116 (1987)
Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)
Tabuchi K, Sakota N, Polym. J., 15, 713 (1983)
Shimada S, Nakagawa K, Tabuchi K, Polym. J., 21, 275 (1989)
Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 22, 777 (1990)
Nishikubo N, Iizawa T, Kobayasi K, Masuda Y, Macromolecules, 16, 722 (1983)
Kondo S, Yasui H, Ohta K, Tsuda K, J. Chem. Soc.-Chem. Commun., 400 (1985)
Nicholas PP, J. Am. Chem. Soc., 109, 155 (1987)
Martinez G, Mijangos C, Terroba P, Millan J, J. Polym. Sci. A: Polym. Chem., 26, 1629 (1988)
Percec S, J. Appl. Polym. Sci., 36, 415 (1988)
Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)
Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, London, p. 106 (1953)
Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 30(5), 612 (1992)

[Referenced By]

[1] Webewr WP, Gokel GW, "Phase Transfer Catalysis in Organic Synthesis," Springer-Verlag, New York (1977)

[2] Starks CM, Liotta C, "Phase Transfer Catalysis-Principle and Techniques," Academic Press, New York (1978)

[3] Dehmlow EV, Dehmlow SS, "Phase Transfer Catalysis," Verlag Chemie, 2nd ed., Weinheim (1983)

[4] Starks CM, "Phase-Transfer Catalysis, New Chemistry, Catalysis, and Applications," Am. Chem Soc., Washington, D.C. (1987)

[5] Imai Y, Abe S, Ueda M, J. Polym. Sci. A: Polym. Chem., 19, 3285 (1981)

[6] Podkoscielny W, Kultys A, J. Appl. Polym. Sci., 26, 1143 (1981)

[7] Yamazaki N, Imai Y, Polym. J., 15, 603 (1983)

[8] Tsai H, Lee Y, J. Polym. Sci. A: Polym. Chem., 25, 1505 (1987)

[9] Kellman R, Willians RF, Dimotsis G, Gerbi DJ, Willians JC, J. Am. Chem. Soc., 109, 128 (1987)

[10] Yamada B, Yasuda Y, Matsudita T, Otsu T, J. Polym. Sci. C: Polym. Lett., 14, 277 (1976)

[11] Reetz MT, Ostarek R, J. Chem. Soc.-Chem. Commun., 213 (1988)

[12] Rasmussen JK, Smith HK, J. Am. Chem. Soc., 103, 730 (1981)

[13] Jayakrishnan A, Shah DO, J. Polym. Sci. A: Polym. Chem., 21, 3201 (1983)

[14] Jayakrishnan A, Shah DO, J. Appl. Polym. Sci., 29, 2937 (1984)

[15] Rasmussen JK, Heilmann SM, Krepski LR, Smith HK, J. Am. Chem. Soc., 109, 116 (1987)

[16] Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)

[17] Tabuchi K, Sakota N, Polym. J., 15, 713 (1983)

[18] Shimada S, Nakagawa K, Tabuchi K, Polym. J., 21, 275 (1989)

[19] Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 22, 777 (1990)

[20] Nishikubo N, Iizawa T, Kobayasi K, Masuda Y, Macromolecules, 16, 722 (1983)

[21] Kondo S, Yasui H, Ohta K, Tsuda K, J. Chem. Soc.-Chem. Commun., 400 (1985)

[22] Nicholas PP, J. Am. Chem. Soc., 109, 155 (1987)

[23] Martinez G, Mijangos C, Terroba P, Millan J, J. Polym. Sci. A: Polym. Chem., 26, 1629 (1988)

[24] Percec S, J. Appl. Polym. Sci., 36, 415 (1988)

[25] Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)

[26] Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, London, p. 106 (1953)

[27] Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 30(5), 612 (1992)