Kinetic Study of Graft Polymerization of Acrylic Acid and Ethyl Methacrylate onto Starch by Ceric Ammonium Nitrate

Document Type : Research Article

Authors

Department of Physical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, I.R. IRAN

Abstract

Graft polymerization of acrylic acid (AA) and ethyl methacrylate (EMA) onto starch (St) were carried out in aqueous solution using ceric ammonium nitrate (CAN) as redox system under N2 atmosphere. The effect of pH, reaction time, temperature, concentrations of CAN, St, and monomers on the graft yield was investigated. Monomer reactivity was in the following order: AA>EMA.The kinetics of the graft polymerization of AA and EMA onto starch in same system with CAN was studied by acid-base and boromometric titration, respectively. The rate expressions for graft polymerization are Rg=k[AA]0.92[CAN]0.56[St]0.46 and R/g=k/[EMA]0.92[CAN]0.53[St]0.48 and a suitable mechanism is suggested. The graft copolymers were investigated by FT-IR spectroscopy. The overall activation energy of graft polymerization of AA onto starch was found to be 36.25 kJ.mol-1 within the temperature range 20-40°C, and for graft polymerization of EMA onto starch is found to be 11.88 kJmol-1 within the temperature range 25-45°C.

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[1] Hebeish, A., EL-Rafie, M. H., Higazy, A. and Ramadan, M. A., Stärke, 44, 101 (1992).
[2] Hebeish, A., EL-Alfy, E. and Bayazeed, A., Starch/ Starke, 40 (5), 191(1988).
[3] Thewlis, B. H., J. Appl. Chem., 13(10), 446 (1963).
[4] Hebeish, A., EL-Rafie, M. H., Higazy, A. and Ramadan, M. A., starch/Stärke, 48(5), 175 (1996).
[5] Rayford, W. E., Wing, R. E. and Doane, W. M., J. Appl. Polym. Sci., 24, 105 (1979).
[6] Maher, G. G., J.Polym. Mater., 11, 85 (1979).
[7] Varma, I. K., Singh, O. P. and Sandle, N. K., Angew. Mokromol. Chem., 119, 183 (1983).
[8] Deshnukh, S. R., Sudhakar, K. and Singh, R. R., J. Appl. Polym. Sci., 43, 1091 (1991).
[9] Okieimen, F. E., Egharevba, F. and Jideaowo, A., Angew Makromol. Chem., 184, 1 (1991).
[10] Bhattacharyya, S. N., Maldas, D., Prog. Polym. Sci., 10, 171 (1984).
[11] Ano, J. P., Liz, C. and Huang, M. Z., J. Appl.  Polym. Sci., 55, 1201 (1995).
[12] Habeish, A., Abd EL- Thalouth, I., EL- Kashouti, M. A. and Abdel Fattah, S. H., Angew. Makromol. Chem., 78, 101 (1979).
[13] Gao, J. P., Tian, R.C., Yu, J. G., et al., J. Appl. Polym. Sci., 53, 1091 (1994).
[14] Mehrotra, R. and Ranby, B., J. Appl. Polym. Sci., 21, 1647 (1977).
[15] Samal, R. K. and Sahoo, P. K., J. Appl. Polym Sci., 29, 309 (1984).
[16] Lenka, S. and Mishra, M., J. Appl. Polym. Sci., 25, 1323 (1980).
[17] Gugliemelli, L. A., Russell, C. R., et al., J. Appl. Polym. Sci., polym. Lett. Ed., 10, 15 (1972).
[18] Mansour, O.Y. and Nagaty, A., Prog. Polym. Sci., 11, 91 (1985).
[19] Brockway, C. E. and Seabery, P. A., J. Polym. Sci., A-I, 5, 1313 (1967).
[20] Fanta, G. F., Russell, R. C. and Rist, C. E., J. Macromol. Sci. Chem., 4, 331 (1970).
[21] Hebeish, A., EL-Rafie, M. H., EL-Kashouti, M. A., EL-Sisi, F., Angew,Makromol.Chem., 93, 97 (1981).
[22] Gaylord, N. G. and Tomono, T., J. Polym. Sci., Polym. Lett. Ed., 13, 689 (1975).
[23] Misra, B. N. and Pande, C. S., J. Polym. Sci., Polym. Chem. Ed., 11, 2369 (1973).
[24] Trimnell, D., Fanta, G.F., J. Polym. Mater., 3, 203 (1992).
[25] Eromosele, I. C., J. Appl. Polym. Sci., 51, 1871 (1994).
[26] Chen, H., Chen, J., Zhang, S., Xibei Shifan Daxue xuebao, 30 (3), 55 (1994) (in chiness).
[27] Mostafa, KH. M., J. App1. Polym. Sci., 56, 263 (1995).
[28] Athawale, V. D., Rathi, S. C., Eu. Polym. J., 33, 1067 (1997).
[29] Trimnell, D., Fanta, G. F., Salch, J. H., J. Appl. Polym. Sci., 60, 285 (1996).
[30] Mino, G. and Kaizerman, S., J. Polym. Sci., 31, 242 (1958).
[31] Fanta, G., Burr, R. C. and Doane, W. M., J. Appl. Polym. Sci., 24, 2015 (1979),
[32] Ceresa, R. J., Ed., wiley- inter Science, New York, P.I, (1977).
[33] Athawale, V. D., Lele, V., Carbohyd. Polym., 35, 21 (1998).
[34] Reves, Z., Rist, C. E. and Russell, C. R., J. Polym. Sci., Part AI, 4, 1031 (1966).
[35] Misra. B. N., Dorga, R. and Kaur, I., J. Polym. Chem. Ed., 18, 341 (1980).
[36] Hoing, D. H. and Merle, E., Starch/ Stärke, 44, 268 (1992).
[37] Yao, K. J. and Tang, Y. B., J. Appl. Polym.  Sci., 45, 349 (1992).
[38] Nagaty, A., Abd- EL- Mouti, F., and Mansour, O. Y., Eur. Polym. J., 16, 343 (1979).
[39] Bayazed, A., Farag, S. and Hebeish, A., Stach/ stärke, 38, (8.5)268 (1986).
[40] Geroge, A., Radhakrishnan, G. and Thomas Joseph, K., J.Appl. polym. Sci., 29, 73 (1984).
[41] Burr, R. C., Fanta, G. F., Doane, W. M. and Russell, C. R., paper presented at the symposium on Flocculation and Stabilization of Solids in Agueous and Nonagueous Media Sponsored by the Chemical Institute of Canada, Turunto (1974).
[42] Panda, A. and Singh, B. C., Polym.-Plast. Technol. Eng., 33, 487 (1996).
[43] Das, N. R., Nayak, N. C., Das, H. K., Mishra, S. N. and Singh, B. C., J.Appl. Polym. Sci, 39, 1979 (1990).
[44] Misra, B. N., Mehta, I. K., et al., J. Polym. Sci. Part A: Polym. Chem., 25, 2117 (1987).
[45] McDowall, D. J., Gupta, B. S. and Stannett, V. T., Prog. Polym., Sci., 10, 1 (1984).
[46] Nayak, P., Lenka, S. and Pati, N., J. Appl. Polym. Sci., 22, 3301 (1978)
[47] Chaimberg, M. and Cohen, Y., AICHE J., 40, 294 (1994).