Rh/SiO2催化剂上双环戊二烯氢甲酰化

采用浸渍法制备了SiO₂低负载量的铑催化剂Rh/SiO₂。研究以三苯基膦为配体的Rh/SiO₂催化剂对双环戊二烯氢甲酰化合成三环癸烷不饱和单醛的催化性能及其影响因素。结果表明，Rh/SiO₂催化剂对双环戊二烯氢甲酰化具有良好的催化作用，双环戊二烯合成三环癸烷不饱和单醛选择性超过99%。双环戊二烯氢甲酰化过程与催化剂用量、三苯基膦浓度、反应压力和反应温度有关。反应过程中存在一定诱导期，随着压力增加，诱导期逐渐缩短；增加催化剂用量和三苯基膦浓度有利于提高双环戊二烯转化率和三环癸烷不饱和单醛收率；升高温度虽然有利于双环戊二烯转化，却降低了三环癸烷不饱和单醛选择性。当催化剂与双环戊二烯质量比为1∶25、三苯基膦浓度10.0 g·L^－1、负载铑质量分数1‰、反应温度110 ℃、反应压力3.0 MPa和反应时间240 min时，双环戊二烯转化率超过99%，三环癸烷不饱和单醛选择性超过99%。

Hydroformylation of dicyclopentadiene on Rh/SiO2 catalysts

Hydroformylation of dicyclopentadiene(DCPD) on Rh/SiO₂ catalysts prepared by an impregnation technique was studied.The results showed that Rh/SiO2 catalysts had effective catalysis for hydroformylation of DCPD to formyltricyclo ［5.2.1.0^2,6］dec-3-ene(MFTD).The effects of various reaction parameters such as catalyst/DCPD mass ratio,PPh₃ concentration,reaction pressure and reaction temperature were investigated.A short induction time was observed in the course of hydroformylation,and it was shorted with the increase of reaction pressure.Increasing the catalyst/DCPD mass ratio and PPh₃ concentration favored DCPD conversion and MFTD yield; increasing the reaction temperature was beneficial to DCPD conversion,but decreased the selectivity to MFTD.DCPD conversion of over 99% and MFTD yield of over 99% were attained under the condition as follows:Rh loading 1‰,catalyst/DCPD mass ratio 1∶25,PPh₃ concentration 10.0 g·L^-1, reaction temperature 110 ℃,reaction pressure 3.0 MPa,and reaction time 240 min.