Kinetic Study of the Oxidation of ε-Caprolactam Impurities with Permanganate for PZ Estimation

Arturo Romero; Aurora Santos; Pedro Yustos; Sergio Rodriguez

Journal of Industrial and Engineering Chemistry, Vol.11, No.1, 88-95, January, 2005

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Kinetic Study of the Oxidation of ε-Caprolactam Impurities with Permanganate for PZ Estimation

Arturo Romero^†, Aurora Santos, Pedro Yustos, and Sergio Rodriguez

Department Ingeniera Qumica, Facultad de Ciencias Qumicas, Universidad Complutense, 28040 Madrid, Spain

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The permanganate number, PZ, is usually used to characterize the behavior of ε-caprolactam during its polymerization. Impurities in ε-caprolactam that are quickly oxidized by permanganate decrease the PZ value and the associated ε-caprolactam quality. To estimated the value of PZ of an ε-caprolactam containing a mixture of different impurities, a knowledge of the kinetics of the reactions involved is necessary. In this study, we obtained the rate laws of the oxidation of some typical ε-caprolactam impurities with permanganate. We added separately to a commercial ε-caprolactam different amounts, ranging from 1 to 3000 ppm, of both commercial (cyclohexylamine, hexylamine, aniline, o-toluidine, p-toluidine, ε-caprolactone, phenol, nitrobenzene, 2-heptylamine, cyclohexanol, cyclohexene, hexylamide, and cyclohexanone oxime) and synthesized impurities (octahydrophenazine, methyl-δ-valerolactam, cyclohexenone oxime, azocyclohepten-2-one, and cyclohexanone oxime). A parallel reaction network is proposed to describe the reactions between the impurities and permanganate and the kinetic parameters have been calculated by fitting the values of PZ obtained experimentally. The PZ value measured for a mixture of impurities was compared to that predicted by using the kinetic parameters, we obtained; a good agreement exists.

Keywords:permanganate number;oxidation;ε-caprolactam;kinetics;impurities

[References]

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Jain SL, Sharma ND, Man-Made Textiles Indian, February, 55 (1997)
Jain SL, Sharma ND, Chem. Abstr. 127, 35816 (1997)
Jodra LG, Romero A, Garcia-Ochoa F, Aracil J, Ind. Eng. Chem. Prod. Res. Dev., 20, 562 (1981)
Jodra LG, Romero A, Garcia-Ochoa F, Aracil J, J. Appl. Polym. Sci., 26, 3271 (1981)
Polo L, Bertuzzi GL, Bovetti E, J. Chromatography, 39, 253 (1969)
Romero A, Yustos P, Santos A, Ind. Eng. Chem. Res., 42(16), 3654 (2003)
Zhao YY, Jing ZZ, Li HP, Zhang HS, Microchem J., 69, 213 (2001)
Allinger NL, Cava M, Organic Chemistry, 1st ed., Worth, New York (1971)
Cotton FA, Wilkinson G, Advanced Inorganic Chemistry, 3rd ed., Wiley, New York (1972)
Rao CN, Ultraviolet and Visible Spectroscopy Chemical Applications, 3rd ed., Butterworths, London (1975)
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Stresinka J, Mokry J, Chemicky Prumysl, 25-50, 30 (1975)
Ho KJ, Geun LS, Suk SM, Hwang LC, Hong LM, Eon PS, U.S. Patent 6245907, June 12, 2001. Chem. Abstr.n131,32249 (2001)
Meng XK, Mu XH, Zong BN, Min E, Zhu ZH, Fu SB, Luo YB, Catal. Today, 79(1-4), 21 (2003)
Fatiadi AJ, Synthesis, 85 (1987)
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Abdel-Hamid MI, Khairou KS, Hassan RM, Eur. Polym. J., 39, 381 (2003)
Damm JH, Hardacre C, Kalin RM, Walsh KP, Water Res., 36, 3638 (2002)
Gardner KA, Mayer JM, Science, 269(5232), 1849 (1995)
Huang KC, Hoag GE, Chheda P, Woody BA, Dobbs GM, Chemosphere, 46, 815 (2002)
Lee DG, Chen T, J. Org. Chem., 56, 5341 (1991)
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El-Khatib RM, Carbohydr. Polym., 47, 377 (2002)
Hood ED, Thomson NR, Grossi D, Farquhar GJ, Chemosphere, 40, 1383 (2000)
Huang KC, Hoag GE, Chheda P, Woody BA, Dobbs GM, J. Hazard. Mater., B87, 155 (2001)
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Kathari CP, Pol PD, Nandibewoor ST, Inorg. React. Mech., 3, 213 (2001)
Kulkarni RM, Bilehal DC, Nandibewoor ST, Inorg. React. Mech., 3, 239 (2001)
Halligudi NN, Desai SM, Nandibewoor ST, Transit. Met. Chem., 26, 28 (2001)
Harihar AL, Kembhavi MR, Nandibewoor ST, Mon. Chem., 131, 739 (2000)

[1] Sheldon RA, VanSanten RA, Catalytic Oxidation: Principles And Applications, pp. 8, 9, 197, World Scientific Publishing, London (1995)

[2] Elmendord J, German Patent 2 106 385 (1971)

[3] Elmendord J, Aug 19. Chem. Abstr., 75, 140355 (1971)

[4] Wiest G, Hopff H, U. S. Patent 2 297 520, Sep 29 (1943)

[5] Wiest G, Hopff H, Chem. Abstr., 37, 1451 (1943)

[6] Capek A, Sb. Vys. Sk. Chem.-Technol., Praze, Technol. Paliv., D33, 339 (1976)

[7] Capek A, Chem. Abstr., 86, 182667 (1977)

[8] Kralicek J, Kondelikova J, Kubaner V, Zamostny Z, Anh LT, Chem. Prum., 24, 620 (1974)

[9] Kralicek J, Kondelikova J, Kubaner V, Zamostny Z, Chem. Abstr. 82, 98440 (1975)

[10] Gankov NP, Russ. J. Appl. Chem., 72, 1810 (1999)

[11] Gankov NP, Chem. Abstr. 132, 238275 (2000)

[12] Jain SL, Sharma ND, Man-Made Textiles Indian, February, 55 (1997)

[13] Jain SL, Sharma ND, Chem. Abstr. 127, 35816 (1997)

[14] Jodra LG, Romero A, Garcia-Ochoa F, Aracil J, Ind. Eng. Chem. Prod. Res. Dev., 20, 562 (1981)

[15] Jodra LG, Romero A, Garcia-Ochoa F, Aracil J, J. Appl. Polym. Sci., 26, 3271 (1981)

[16] Polo L, Bertuzzi GL, Bovetti E, J. Chromatography, 39, 253 (1969)

[17] Romero A, Yustos P, Santos A, Ind. Eng. Chem. Res., 42(16), 3654 (2003)

[18] Zhao YY, Jing ZZ, Li HP, Zhang HS, Microchem J., 69, 213 (2001)

[19] Allinger NL, Cava M, Organic Chemistry, 1st ed., Worth, New York (1971)

[20] Cotton FA, Wilkinson G, Advanced Inorganic Chemistry, 3rd ed., Wiley, New York (1972)

[21] Rao CN, Ultraviolet and Visible Spectroscopy Chemical Applications, 3rd ed., Butterworths, London (1975)

[22] Romero A, Santos A, Yustos P, Ind. Eng. Chem. Res., in press (2004)

[23] Stresinka J, Mokry J, Chemicky Prumysl, 25-50, 30 (1975)

[24] Ho KJ, Geun LS, Suk SM, Hwang LC, Hong LM, Eon PS, U.S. Patent 6245907, June 12, 2001. Chem. Abstr.n131,32249 (2001)

[25] Meng XK, Mu XH, Zong BN, Min E, Zhu ZH, Fu SB, Luo YB, Catal. Today, 79(1-4), 21 (2003)

[26] Fatiadi AJ, Synthesis, 85 (1987)

[27] Walton J, Labine P, Reidies, in W. W. Eckenfelder, A. R. Bowers, and J. A., Roth, Eds., Chemical Oxidation. Lancaster, Basel: Technomic Publishing, p. 205 (1991)

[28] Abdel-Hamid MI, Khairou KS, Hassan RM, Eur. Polym. J., 39, 381 (2003)

[29] Damm JH, Hardacre C, Kalin RM, Walsh KP, Water Res., 36, 3638 (2002)

[30] Gardner KA, Mayer JM, Science, 269(5232), 1849 (1995)

[31] Huang KC, Hoag GE, Chheda P, Woody BA, Dobbs GM, Chemosphere, 46, 815 (2002)

[32] Lee DG, Chen T, J. Org. Chem., 56, 5341 (1991)

[33] Panari RG, Chougale RB, Nandibewoor ST, J. Phys. Org. Chem., 11, 448 (1998)

[34] Panari RG, Nandibewoor ST, Synth. React. Inorg. Metal Org. Chem., 29, 1539 (1999)

[35] Rankin KN, Liu Q, Hendry J, Yee H, Noureldin NA, Lee DG, Tetrahedron Lett., 39, 1095 (1998)

[36] Shukla R, Sharma PK, Kotai L, Banerji K, Proc. Ind. Acad. Sci. Chem. Sci., 115, 129 (2003)

[37] Hidefumi S, Makoto T, Yu K, Kouji T, Toshio U, E. Patent 0785188A1, July 23 (1997)

[38] Hidefumi S, Makoto T, Yu K, Kouji T, Toshio U, Chem. Abstr. 126, 171497 (1997)

[39] Freeman F, Chem. Rev., 75, 439 (1975)

[40] Marquardt DL, J. Soc. Ind. Appl. Math., 11, 431 (1963)

[41] El-Khatib RM, Carbohydr. Polym., 47, 377 (2002)

[42] Hood ED, Thomson NR, Grossi D, Farquhar GJ, Chemosphere, 40, 1383 (2000)

[43] Huang KC, Hoag GE, Chheda P, Woody BA, Dobbs GM, J. Hazard. Mater., B87, 155 (2001)

[44] Sheeba PS, Nair TDR, Indian J. Chem. Sect. A Inorg. Bio Inorg. Phys. Theo. Anal. Chem., 40, 610 (2001)

[45] Wiberg KB, Freeman F, J. Org. Chem., 65, 573 (2000)

[46] Yan YE, Schwartz FW, J. Contam. Hydrol., 37, 343 (1999)

[47] Bilehal DC, Kulkarni RM, Nandibewoor ST, J. Res. Phys. Chem. Chem. Physics, 217, 1 (2003)

[48] Kathari CP, Pol PD, Nandibewoor ST, Inorg. React. Mech., 3, 213 (2001)

[49] Kulkarni RM, Bilehal DC, Nandibewoor ST, Inorg. React. Mech., 3, 239 (2001)

[50] Halligudi NN, Desai SM, Nandibewoor ST, Transit. Met. Chem., 26, 28 (2001)

[51] Harihar AL, Kembhavi MR, Nandibewoor ST, Mon. Chem., 131, 739 (2000)