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http://dx.doi.org/10.9713/kcer.2013.51.3.394

Synthesis of Cyclododecatriene from 1,3-Butadiene by Trimerization over Amine-Titanium Complex Catalyst  

Park, Da Min (Department of Chemical Engineering, Inha University)
Kim, Gye-Ryeong (Department of Chemical Engineering, Inha University)
Lee, Ju Hyun (Department of Chemical Engineering, Inha University)
Cho, Deuk Hee (Korea Research Institute of Chemical Technology)
Kim, Geon-Joong (Department of Chemical Engineering, Inha University)
Publication Information
Korean Chemical Engineering Research / v.51, no.3, 2013 , pp. 394-402 More about this Journal
Abstract
The new complex catalysts were synthesized by the reaction of titanium compounds (titanium chloride or titanium butoxide) and diamines in this work, and they showed very high catalytic activities for the cyclododecatriene (CDT) synthesis from 1,3-butadiene through trimerization. CDT synthetic reaction was performed in an autoclave reactor, and the effects of reaction temperature, type of catalyst, catalyst amount added into the system, the mole ratio of Al/Ti and immobilization method were investigated on the yield of product CDT. The titanium complex catalyst combined to diamine with 1:1 ratio showed high selectivity to CDT more than 90%. The ratio of TTT-CDT/TTC-CDT isomers in the product revealed as different values, depending on the type of diamine combined to titanium and Ti/diamine ratios. Those homogeneous complexes could be used as a heterogenized catalyst after anchoring on the supports, and the immobilized titanium catalyst retained the catalytic activities for several times in the recycled reactions without leaching. The carbon support containing titanium has exhibited superior activity to the silica support. Especially, when the titanium complex was anchored on the support which was fabricated by the hydrolysis of tripropylaminosilane itself, the resulting titanium catalyst showed the highest BD conversion and CDT selectivity.
Keywords
Butadiene; Cyclododecatriene; Titanium Complex Catalyst; Immobilization; Diamine;
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1 Moberg, C. and Rakos, L., "Polymer-supported 2,2'-dipyridylmethane: Catalytic Activity of Transition Metal Complexes in Hydrogenations and Oligomerizations," J. Organomet. Chem., 335(1), 125- 31(1987).   DOI   ScienceOn
2 Takahasi, H. and Yamaguchi, M., "Synthesis of 1,5,9-cyclododecatriene," J. Org. Chem., 28, 1409-1411(1963).   DOI
3 Polacek, J. et al. "Titanium-catalyzed Cyclotrimerization of Butadiene: I. Arenetitanium(II) Chloro- and Bromo-alane Complexes," J. of Mol. Catal., 29(2), 165-80(1985).   DOI   ScienceOn
4 Diel, B. N., Han, M. and White, J. M., "Synthesis of [14C6-3,4,7,8,11,12]-(1E,5E,9E)-cyclododeca-1,5,9-triene," J. Label. Compd. Radiopharm., 50, 407-409(2007).   DOI   ScienceOn
5 Ube industry, "The method of Cyclododecatriene Synthesis," JP2002-161054(2002).
6 Ube industry, "The method of Cyclododecatriene Synthesis," JP2002-60353(2002).
7 Ube industry, "The method of Cyclododecatriene Synthesis," JP2005-132770(2002).
8 Ube industry, "The method of Cyclododecatriene Synthesis," JP2002-139144(2002).
9 Herwig, J., Bruuing, W., Roos, M. and Wilczok, N., "Process for Preparing Cyclododecatriene," US 0265184(2007).
10 Wilczok, N., Schiffer, T. and Wiedenbusch, P., "Process for Preparing Cyclododecatrienes with Recycling of the Catalyst," US 6403851 B1(2002).
11 Shearer, A. S., Miguel, Y. R., Minich, E. A., Pochan, D. and Jenny, C., "Polymer-supported Metallocene Catalysts for Ethylene Polymerization: Characterization and Catalytic Studies," Inorganic Chem. Comm., 10, 262-264(2007).   DOI   ScienceOn