Abstract:

The oligomerization of endodicyclopentadiene（endo-DCPD）in a continuousflow reactor at elevated pressure was studied to produce tricyclopentadiene（TCPD）that was the precursor of highenergydensity fuelThe composition of the products and possible reaction pathway were analyzed，and the effects of reaction conditions were evaluatedCompared with the batchwise reaction at atmospheric pressure，the continuousflow process could significantly enhance the reaction，increase the exo/endo ratio of TCPD，and produce a new product exo-DCPDThe exo/endo ratio was linearly dependent on the selectivity of exo-DCPDA high pressure of above 1.2 MPa was necessary to facilitate the reactionThe conversion of endo-DCPD increased with the increase of temperature，while the yield of TCPD reached the highest value at 160℃But the exo/endo ratio decreased with the increase of temperatureThe conversion of DCPD and the yield of TCPD increased when the residence time was increased，but the reaction rate decreasedA short residence time was favorable，because it led to a high exo/endo ratio for TCPDThe effect of feed concentration was limitedUnder the optimal condition，the conversion of endoDCPD was 82.2% and the yield of TCPD was 41.7%.

摘要：

为制备密度大于1 g·ml^-1的高密度燃料母体化合物三环戊二烯（TCPD），研究了双环戊二烯（DCPD）的加压连续聚合反应。分析了聚合反应产物组成和反应途径，研究了反应条件的影响。与常压间歇反应相比，加压连续反应能极大地提高反应转化率和收率，优化产物组成，TCPD中挂式/桥式（exo/endo）比例大大提高，并生成新的产物exo-DCPD。反应途径分析表明，TCPD中exo/endo比例与exo-DCPD选择性呈线性正相关。研究发现，为维持反应进行压力应不低于1.2 MPa，增加温度能提高反应转化率，而TCPD最高收率出现在160℃，TCPD的exo/endo比例随温度增加而降低，反应转化率和收率随停留时间增加而增加，但转化速率降低，缩短停留时间有利于提高TCPD的exo/endo比例，浓度对反应影响不大。在较优条件下，endo-DCPD转化率达82.2%，TCPD收率达41.7%。