SBS选择性催化加氢动力学研究

Kinetic studies of SBS catalytic hydrogenation with high selectivity

以双环戊二烯二氯化钛 (Cp2 TiCl2 )为主催化剂 ,邻苯二甲酸二甲酯 (DMP)为助催化剂研究了苯乙烯 丁二烯嵌段共聚物选择性催化加氢动力学。在 76℃、适宜的氢气压力以及主、助催化剂浓度下进行SBS加氢动力学研究得到动力学方程为 - d[c(CC ) ]dt =kc1 (CC )p1 ,1 2 (H2 )c1 (Ti )c-2 (DMP) ,相应的在 70～ 84℃范围内加氢反应活化能为 83 4 8kJ/mol。对加氢产物微观结构分析表明该催化体系加氢效率高 ,选择性高 ,且对SBS中PB链段1 ,2 结构和反式 1 ,4 结构先加氢 。

The kinetic behavior of hydrogenation of styrene butadiene styrene tri block copolymers (SBS, S/B=3/7,linear) using the bis (cyclopentadineyl) titanium dichloride (Cp 2TiCl 2) as a catalyst and dimethyl ( o ) phthialate (DMP) as a cocatalyst was systematically studied. It was showed that the catalysts had a high activity and a high selectivity with phenyl not being hydrogenated. The kinetics equation of hydrogenation,which was obtained with proper concentrations of the catalyst and the cocatalyst at 76?℃ and under proper H 2 pressure, was -d[ c (CC)]d t = kc 1(CC) p 1 12 (H 2) c 1(Ti *) c -2 (DMP), and the activation energy of hydrogenation between 70～84?℃ was 83 48?kJ/mol. The structures of the products were also studied by 1H NMR spectra. The result indicated that 1,2 PB units and trans 1,4 PB units were hydrogenated prior to cis-1,4-PB units, and were fully hydrogenated.