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

The new complex catalysts were synthesized by the reaction of titanium compounds (titanium chlorideor 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 autoclavereactor, and the effects of reaction temperature, type of catalyst, catalyst amount added into the system, themole ratio of Al/Ti and immobilization method were investigated on the yield of product CDT. The titanium complexcatalyst 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 titaniumand Ti/diamine ratios. Those homogeneous complexes could be used as a heterogenized catalyst after anchoringon the supports, and the immobilized titanium catalyst retained the catalytic activities for several times in therecycled reactions without leaching. The carbon support containing titanium has exhibited superior activity to the silicasupport. Especially, when the titanium complex was anchored on the support which was fabricated by the hydrolysisof tripropylaminosilane itself, the resulting titanium catalyst showed the highest BD conversion and CDTselectivity.