Rh/SiO_2催化剂上双环戊二烯氢甲酰化

Hydroformylation of dicyclopentadiene on Rh/SiO_2 catalysts

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 （DCPD） on Rh/SiO2 catalysts prepared by an impreg- nation technique was studied. The results showed that Rh/SiO2 catalysts had effective catalysis for hydro- formylation of DCPD to formyltricyelo [ 5.2.1.02＇6 ] dec-3-ene （MFFD）. The effects of various reaction parameters such as catalyst/DCPD mass ratio, PPh3 concentration, reaction pressure and reaction tempera- ture 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 concen- tration 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 MFFD yield of over 99% were attained under the condition as follows：Rh loading 1%o, 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.