Tricaprylmethylammonium Chloride에 의한 Acrylonitrile과 Methylmethacrylate의 라디칼 공중합(I)-공중합 반응속도론-

박상욱; 박대원; 이성수; 양삼석; 백재진

HWAHAK KONGHAK, Vol.34, No.2, 215-222, April, 1996

Radical Copolymerization of Acrylonitrile and Methylmethacrylate with Phase Transfer Tricaprylmethylammonium Chloride(I)-Reaction Kinetics-

박상욱, 박대원, 이성수, 양삼석, 백재진

초록

회분식 고분자 중합반응기에서 Na₂S₂O₄ 수용액상과 CCl₄ 유기상 접촉계면을 통한 액-액 불균일상계에서 tricaprylmethyl-ammonium chloride 상이동촉매를 사용하여 25℃, 질소기류하에서 acrylonitrile과 methylmethacrylate 단량체의 공중합 반응 실험을 행하여 초기 공중합속도를 측정하였다. 초기 공중합속도는 상이동촉매와 Na₂S₂O₄의 초기 농도항으로 나타내기보다는 수용액상에 존재하는 상이동촉매와 S₂O₄^-2 이온농도가 결합된 항으로 나타낸 [Q⁺]_w[S₂O₄^-2]_w^1/2와 CCl₄의 제곱근과 단량체의 공급농도비에 정비례하였다. 측정한 초기 공중합속도를 사용하여 액-액 불균일계 접촉계면을 통한 공중합 반응기구를 해석하였다.

The phase-transfer radical copolymerization of acrylonitrile with methylmethacrylate by tricaprylmethyl-ammonium chloride were investigated in a Na₂S₂O₄ aqueous-CCl₄ organic two-phase system at 25℃ and under nitrogen atmosphere. The initial rate of copolymerization was found to be proportional to the concentration of [Q⁺]_w, [S₂O₄^-2]_w^1/2,[CCl₄]_Ø^1/2 and the molar ratio of feed of monomers. The observed initial rates of copolymerization were used to analyzed the copolymerization mechanism proposed with a cyclic phase-transfer initiation step.

Keywords:Phase Transfer Catalyst;Copolymerization;Tricaprylmethylammonium Chloride

[References]

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Starks CM, Liotta C, "Phase Transfer Catalysis-Principle and Techniques," Academic Press, New York (1978)
Dehmlow EV, Dehmlow SS, "Phase Transfer Catalysis," 2nd Ed Verlag Chemie, Weinheim (1983)
Starks CM, "Phase-Transfer Catalysis, New Chemistry, Catalysis, and Applications," Am. Chem. Soc. Washington D.C. (1987)
Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 31(1), 107 (1993)
Park SW, Moon JB, Jung YH, Park DW, Shin JH, HWAHAK KONGHAK, 32(2), 222 (1994)
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, Dimotis 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)
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Jayakrishnan A, Shah DO, J. Polym. Sci. A: Polym. Chem., 21, 3201 (1983)
Jayakrishnan A, Shah DO, J. Appl. Polym. Sci., 29, 2937 (1984)
Ramussen JK, Heilman 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)
Park SW, Moon JB, Ha YS, Lim GT, Polymer, 17, 100 (1993)
Park SW, Moon JB, Ha YS, Kim JH, J. Korean Ind. Eng. Chem., 4(2), 300 (1993)
Park SW, Kaseger CF, Baek JJ, Polym.(Korea), 19(1), 1 (1995)
Park SW, Kaseger CF, Baek JJ, Yang SS, HWAHAK KONGHAK, 33(1), 79 (1995)
Tabuchi K, Sakota N, Polym. J., 15, 713 (1983)
Shimada S, Nakagawa K, Taguchi 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)
Percer S, J. Appl. Polym. Sci., 36, 415 (1988)
Bulacovschi V, Mihailescu C, Ioan S, Simionescu BC, J. Macromol. Sci.-Chem., A28, 613 (1991)
Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)
Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 30(5), 612 (1992)
Seymour RB, Carrher CE, "Polymer Chemistry," New York, p. 320 (1981)
Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, London, p. 106 (1953)
Dehmlow EV, Dehmlow SS, "Phase Transfer Catalyst," 3rd Edition, VCH Publishers, Inc., New York, p. 73 (1993)

[Referenced By]

[1] Weber WP, Gokel WG, "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," 2nd Ed Verlag Chemie, Weinheim (1983)

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

[5] Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 31(1), 107 (1993)

[6] Park SW, Moon JB, Jung YH, Park DW, Shin JH, HWAHAK KONGHAK, 32(2), 222 (1994)

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

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

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

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

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

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

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

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

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

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

[17] Ramussen JK, Heilman SM, Krepski LR, Smith HK, J. Am. Chem. Soc., 109, 116 (1987)

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

[19] Park SW, Moon JB, Ha YS, Lim GT, Polymer, 17, 100 (1993)

[20] Park SW, Moon JB, Ha YS, Kim JH, J. Korean Ind. Eng. Chem., 4(2), 300 (1993)

[21] Park SW, Kaseger CF, Baek JJ, Polym.(Korea), 19(1), 1 (1995)

[22] Park SW, Kaseger CF, Baek JJ, Yang SS, HWAHAK KONGHAK, 33(1), 79 (1995)

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

[24] Shimada S, Nakagawa K, Taguchi K, Polym. J., 21, 275 (1989)

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

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

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

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

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

[30] Percer S, J. Appl. Polym. Sci., 36, 415 (1988)

[31] Bulacovschi V, Mihailescu C, Ioan S, Simionescu BC, J. Macromol. Sci.-Chem., A28, 613 (1991)

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

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

[34] Seymour RB, Carrher CE, "Polymer Chemistry," New York, p. 320 (1981)

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

[36] Dehmlow EV, Dehmlow SS, "Phase Transfer Catalyst," 3rd Edition, VCH Publishers, Inc., New York, p. 73 (1993)