Kinetic study of cis-polybutadiene epoxidation by using 1HNMR spectroscopy in buffered oxone® solution with tetra-n-butyl ammonium bromide as phase transfer catalyst (PTC)


Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran


Cis-polybutadiene was functionalized using in–situ generated DMD as oxidant and tetra-n-butyl ammonium bromide as phase transfer catalyst (PTC). The epoxidation process was investigated by 1HNMR spectroscopy. 1HNMR spectrum analysis of products confirms the absence of ring opening side products in epoxidation reaction. Various factors such as reaction temperature, reaction time and the concentrations of oxidant, PTC and polymer are also examined in detail. Kinetic study showed that the catalytic epoxidation reaction of cis-polybutadiene is first-order with respect to double bonds and activation energy for the reaction is 22.82 KJ/mol.


[1] J.P. Arlie, Synthetic Rubbers Processes and Economic Data. Technip, Paris, 1992.
[2] H. Kaczmarek, Polym. Bull. 34 (1995) 211-218.
[3] X.H. Wang, H.X. Zhang, Z.G. Wang, B.Z. Jiang, Polymer. 38 (1997) 5407-5410.
[4] T. Tatsumi, M. Misono, T. Murahashi, Green Chemistry-Chemistry toward a Sustainable Society, Kodoansha, Tokyo, 2001.
[5] D. Swern, G.N. Billen, T.W. Findley, J.T. Scanlan, J. Am. Chem. Soc. 67 (1945) 1786-1789.
[6] J.M. Yang, H.T. Lin, W.C. Lai, J. Memb. Sci. 208 (2002) 105-117.
[7] X. Jian, A.S. Hay, J. Polm. Sci. Polym. Chem. 29 (1991) 1183-1189.
[8] E. Kaczmarczyk, E. Janus, E. Milchert, J. Mol. Cata. A: Chemical 235 (2005) 52-56.
[9] M.J. Tornaritis, A.G. Coutsolelos, J. Polym. 33 (1992) 1771-1772.
[10] X.G. Jian, A.S. Hay, J. Polym. Sci.: Part C: 28 (1990) 285-288.
[11] M.M. Alavi Nikje, A. Rafiee, M. Haghshenas, Malaysian Chemical Congress (MCC), 2004.
[12] F.H. Rajabi, M.M. Alavi Nikje, B.V. Farahani, N. Sabouri, Designed Monomers Polymers 9 (2006) 383-392.