Abstract:

The hydrogenated product of tricyclopentadiene (TCPD) is a potential high-energy-density fuel.The hydrogenation pathway of TCPD was investigated to understand the reaction process.The reaction intermediate and final products were characterized by using GC-MS, IR, 1H NMR and 13C NMR.The double bond in norbornene ring (NB bond) of TCPD was easily saturated at a low temperature, and an intermediate 12,13-dihydrotricyclopentadiene (12,13-DHTCPD) was formed.Higher temperature and hydrogen pressure were required for the saturation of remaining double bond in cyclopentene ring (CP bond) to generate a completely hydrogenated compound tetrahydrotricyclopentadiene (THTCPD).That is to say, the reaction occurred via the TCPD→12,13-DHTCPD→THTCPD route.To clarify the reactivity of double bonds in TCPD molecules, a DFT calculation at B3LYP/6-31G* level was conducted by using Gaussian 03 series programs.The bond parameters confirmed that the NB double bond was more reactive than the CP bond.Total energy calculation also showed that 12,13-DHTCPD was preferred in thermodynamics, compared with another possible intermediate 5,6-DHTCPD.The computational result was in good agreement with the experiments.This work provides fundamental information for the two-step hydrogenation operation of TCPD.

摘要：

三环戊二烯(TCPD)的加氢产物是具有重要应用价值的高密度碳氢燃料，本文对三环戊二烯的加氢反应过程进行了研究。采用气质联用、红外光谱和核磁共振对加氢产物进行表征，发现在加氢反应中TCPD的降冰片烯(NB)双键首先被饱和，生成中间产物 12,13-二氢三环戊二烯(12,13-DHTCPD)，残留的环戊烯 (CP)双键需要在更高的温度和氢压下反应生成四氢三环戊二烯(THTCPD)，即反应按照TCPD→12,13-DHTCPD→THTCPD的途径进行。利用密度泛函理论中的B3LYP/6-31G*方法对加氢过程进行模拟，证实TCPD中NB双键比CP双键更活泼，反应活性更高，并且NB双键加氢产物比CP双键加氢产物在热力学上更稳定，因此反应中NB双键优先反应，从理论上证实了实验结果。研究为三环戊二烯的两段加氢工艺提供了理论依据。