Tricaprylmethylammonium Chloride에 의한 Acrylonitrile과 Methylmethacrylate의 라디칼 공중합(II)-단량체 반응성비-

박상욱; 박대원; 이성수; 양삼석; 백재진

HWAHAK KONGHAK, Vol.34, No.2, 223-229, April, 1996

Redical Copolymerization of Acrylonitrile and Methylmethacrylate with Phase Transfer Tricaprylmetylammonium Chloride(II)-Monomer Reactivity Retio-

박상욱, 박대원, 이성수, 양삼석, 백재진

초록

회분식 고분자중합 반응기에서 NaS₂O₄ 수용액상과 CCl₄유기상 접촉계면을 통한 액-액 불균일상계에서 tricaprylmethyl-ammonium chloride 상이동촉매를 사용하여 25℃, 질소기류하에서 acrylonitrile과 methylmethacrylate단량체의 공중합 반응을 행하여 초기 공중합 반응속도를 측정하였다. 측정된 초기 공중합속도를 사용하여 액-액 불균일계 접촉계면을 통한 공중합 반응에서 공중합 반응기구를 해석하였으며, 이로부터 단량체의 반응성비를 구하였다. 재래적으로 사용하는 Kelen-Tudos법 및 Fineman-Ross 법으로 구한 값과 비교하였으며, M₁과M₂ 에 대한 반응성비는 각각 0.11과 2.30이었다.

The phase-transfer radical copolymerization of acrylonitrile with methylmethacrylate by tricaprylmethyl-ammonium chloride were investigated in Na₂S₂O₄ aqueous-CCl₄ organic two-phase system at 25℃ and under nitrogen atmosphere. The monomer reactivity ratios, r₁ and r₂ were obtained by the copolymerization mechanism with a cyclic phase-transfer initiation step and compared with those obtained by using the Kelen-Tudos method and Fineman-Ross method. Their values were 0.11 and 2.30, respectively.

Keywords:Phase Transfer Catalyst;Copolymerization;Monomer Reactivity Ratio

[References]

Weber WP, Gokel WG, "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," 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, Matsushita 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)
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)
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)
Percer S, J. Appl. Polym. Sci., 36, 415 (1988)
Bulacovschi V, Mihailescu C, Loan S, Simionescu BC, J. Macromol. Sci.-Chem., A28, 613 (1991)
Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)
Seymour RB, Carrher CE, "Polymer Chemistry," New York, p. 320 (1981)
Park SW, Moon JB, Ha YS, Lim GT, Polym.(Korea), 17(1), 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)
Park SW, Park DW, Lee SS, Yang SS, Baek JJ, HWAHAK KONGHAK, to be summitted (1995)
Kelen T, Tudos F, J. Macromol. Sci.-Chem., A9(1), 1 (1975)
Barb WG, J. Polym. Sci., 37 (1959)
Mayo FR, Walling C, Chem. Rev., 46, 191 (1950)
Walling C, J. Am. Chem. Soc., 71, 1930 (1949)
Brandrup J, Immergut EH, "Polymer Handbook," 2nd Edition, John Wiley & Sons, Inc., New York, P II 250 (1975)

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

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

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

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

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

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

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

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

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

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

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

[30] Park SW, Moon JB, Ha YS, Lim GT, Polym.(Korea), 17(1), 100 (1993)

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

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

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

[34] Park SW, Park DW, Lee SS, Yang SS, Baek JJ, HWAHAK KONGHAK, to be summitted (1995)

[35] Kelen T, Tudos F, J. Macromol. Sci.-Chem., A9(1), 1 (1975)

[36] Barb WG, J. Polym. Sci., 37 (1959)

[37] Mayo FR, Walling C, Chem. Rev., 46, 191 (1950)

[38] Walling C, J. Am. Chem. Soc., 71, 1930 (1949)

[39] Brandrup J, Immergut EH, "Polymer Handbook," 2nd Edition, John Wiley & Sons, Inc., New York, P II 250 (1975)