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Tricaprylmethylammonium Chloride에 의한 Acrylonitrile과 Methylmethacrylate의 라디칼 공중합(I)-공중합 반응속도론-
Radical Copolymerization of Acrylonitrile and Methylmethacrylate with Phase Transfer Tricaprylmethylammonium Chloride(I)-Reaction Kinetics-
HWAHAK KONGHAK, April 1996, 34(2), 215-222(8), NONE
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Abstract
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]w1/2와 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]w1/2,[CCl4]Ø1/2 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.
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Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305 (1991)
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Tabuchi K, Sakota N, Polym. J., 15, 713 (1983)
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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)
