[Ti(OC4H9)4/2,5-Dimethoxytetrahydrofuran/ TEA/Ethylene Chlorobromide] as a Novel Homogeneous Catalyst System Effective for the Ethylene Dimerization Reaction

In the present research, the titanium-catalyzed ethylene dimerization and more specifically, the concomitant byproducts and polymer formation have been studied in the presence of 2,5-dimethoxytetrahydrofuran as an electron donor compound in the combination with triethylaluminium (TEA) as activator. Then, we added ethylene chlorobromide as a new efficient promoter to the relevant catalyst system. Finally, the behavior of novel homogeneous [Titanium tetrabutoxide (Ti(OC4H9)4)/2,5-dimethoxytetrahydrofuran/ TEA/ethylene chlorobromide] was investigated in the various operating conditions for the optimum production of 1-butene. In the optimum conditions, a very high ethylene conversion (almost 90.77 %), a relative high selectivity to 1-butene (79.00 %), yield of reaction equal to 71.70 % and a significant productivity (turnover frequency equal to 1370 h-1) were achieved.




References:
[1] G. P. Blov, P. E. Mathkovsky, "Process for the production of higher ╬▒-
olefins", Petrol. Chem., vol. 50, 2010, pp. 283-289.
[2] A. W. Al-Sadoun, "Dimerization of ethylene to butene-1 catalyzed by Ti
(OR-) 4-AlR3", Appl. Catal. A: General, vol. 105, 1993, pp. 1-40.
[3] A. M. Al-Jaralleh, J. A. Anabtawi, M. A. B. Siddiqui, A. M. Aitani, "Ethylene dimerization and oligomerization to butene-1 and linear alphaolefins;
A review of catalytic system and processes", Catal. Today, vol. 14, 1992, pp. 1-124.
[4] V. I. Zhukov, G. V. Val kovich, B. N. Shorik, Yu. M. Petrov., G. P.
Blov, "Selective dimerization of ethylene to butene-1 under the conditions of industrial process, I. Influence of temperature and pressure
on the rate of the process in a bubbling type reactor", Russ. J. Appl. Chem., vol. 80, 2007, pp. 1195-1200.
[5] S. M. Pillai, G. L. Tembe, M. Ravindranathan, S. Sivaram, "Dimerization of ethylene to 1-butene catalyzed by titanium alkoxidetrialkylaluminum
system", Ind. Eng. Chem. Res., vol. 27, 1988, pp.
1971-1977.
[6] H. K. Leo, D. G. Li, S. Li, "The effect of halide and the coordination geometry of chromium center in homogeneous catalyst system for ethylene trimerization", Mol. Catal. A: Chemical, vol. 221, 2004, pp. 9-17.
[7] H. Mahomed, A. Bollmann, J. T. Dixon, V. Gokuln, L. Griesel, C. Grove, F. Hess, H. Maumela, L. Pepler, "Ethylene trimerization catalyst
based on substituted cyclopentadienes", Appl. Catal. A: General, vol.
193, 2003, pp. 355-359.
[8] Y. Yang, H. Kim, J. Lee, H. Paik, H. G. Jang, "Roles of chloro compound in homogeneous [Cr(2-ethyhexanoate)3/2,5-dimethylpyrrole/
triethylaluminum/chloro compound] catalyst sysytem for ethylene trimerization", Appl. Catal. A: General, vol. 193, 2000, pp. 29-38.
[9] H. Chen, X. Liu, W. Hu, Y. Ning, T. Jian, "Effects of halide in homogeneous Cr(III)/PNP/MAO catalytic systems for ethylene
tetramerization toward 1-octene", Mol. Catal. A: Chemical, vol. 270,
2007, pp. 273-277.
[10] F. A. Carey, R. J. Sunderberg, "Advanced Organic Chemistry", 3rd ed.
part A: structure and mechanisms, Plenum Press, New York, 1990, ch.
3, p. 144.
[11] E. Killian, K. Blann, A. Bollmann, J. T. Dixon, S. Kuhlmann, M. C.
Maumela, H. Maumela, D. H. Morgan, P. Nongodlwana, M. J. Overett,
M. Pretorius, K. Höfener, P. Wasserscheid, "The use of
bis(diphenylphosphino) amines with N-aryl functionalities in selective
ethylene tri- and tetramerisation", Mol. Catal. A: Chemical, vol. 270,
2007, pp. 214-218.
[12] H. T. Jiang, Y. Ning, B. Zhang, J. Li, G. Wang, J. Yi, Q. Huang,
"Preparation of 1-octene by the selective tetramerization of ethylene",
Mol. Catal. A: Chemical, vol. 259, 2006, pp. 161-165.
[13] C. P. Christenson, J. A. May, L. E. Freyer in R. P. Quirk (editor),
"Transition metal catalyzed polymerization: alkenes and dienes",
Harwood Academic, New York, 1983, p. 763.
[14] T. W. Woo, S. I. Woo, "Kinetics study of ethylene dimerization
catalyzed over Ti (O-nC4H9)4/AlEt3" , J. Catal., vol. 132, 1991, pp. 68-78.