均相铑膦催化体系下1-癸烯氢甲酰化反应研究

氢甲酰化反应是目前生产醛醇化合物最重要的反应之一,高碳烯烃氢甲酰化工艺改进是研究的难点和热点之一。探索了一种C10烯烃氢甲酰化反应的工艺,以三苯基膦（Ph₃P）和亚磷酸三（2-叔丁基-4-甲氧基苯基）酯（L_A）混合物为配体,与乙酰丙酮二羰基铑原位合成的催化体系催化1-癸烯氢甲酰化反应。系统考察了反应温度、反应压力、铑浓度、膦铑比、无机盐添加剂对反应的影响。结果表明,在n（Ph₃P）/n（L_A）=10、铑质量分数为280 mg/kg,1-癸烯用量（相对于甲苯）为0.3 g/mL,n（膦）/n（铑）=45、反应温度为90 ℃、反应压力为2.0 MPa、n（一氧化碳）/n（氢气）=1条件下反应4 h,1-癸烯转化率为98.1%、醛收率为93.2%、正异比为7.5。研究还发现,在减压蒸馏产物与催化剂分离时,加入无机盐添加剂能够提高催化剂的稳定性,减少铑损失。

Study on hydroformylation of 1-decene catalyzed by homogeneous rhodium phosphine

Hydroformylation is one of the most important reactions for the production of aldehydes and alcohols,and the improvement of hydroformylation process of high olefins has been one of the difficulties and hotspots in the research.A hydroformylation process of C10 olefin was explored.A mixture of triphenylphosphine and tris(2-tert-butyl-4-methoxyphenyl)phosphite was used as the ligand to react with dicarbonylacetylacetonato rhodium(Ⅰ)to form the in-situ synthesis catalyst system for hydroformylation of 1-decene.The effects of reaction temperature,pressure,Rh concentration,phosphine/Rh ratio and inorganic salt additive on the reaction were investigated.The results showed that under the conditions of n(Ph₃P)/n(L_A)=10,Rh concentration of 280 mg/kg,1-decene of 0.3 g/mL(toluene),n(P)/n(Rh)=45,reaction temperature of 90℃,pressure at2.0 MPa,n(CO)/n(H₂)=1,reaction time of 4 h,the conversion of 1-decene was 98.1%and the yield of aldehydes was 93.2%with N/I of 7.5.It is also found that when the product is separated from the catalyst by vacuum distillation,the addition of inorganic salt can improve the stability of the catalyst and reduce the loss of rhodium.