高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (2): 279.

• 研究论文 • 上一篇    下一篇

新型膦配体PDBPDS在氢甲酰化反应中催化剂配体性能的研究

张敬畅, 严斌, 曹维良, 李江波   

  1. 北京化工大学理学院, 北京 100029
  • 收稿日期:2001-01-18 出版日期:2002-02-24 发布日期:2002-02-24
  • 通讯作者: 曹维良(1943年出生),男,教授,从事催化及量化研究.E-mail:Caowl@mail.buct.edu.cn E-mail:Caowl@mail.buct.edu.cn
  • 基金资助:

    国家"九五"科技攻关项目(96-A12-04-05);国家自然科学基金(批准号:20076004);教育部博士点基金(批准号:2000001005)资助

Performance of a Novel Phosphonium Ligand PDBPDS in Hydroformylation Reaction

ZHANG Jing-Chang, YAN Bin, CAO Wei-Liang, LI Jiang-Bo   

  1. College of Science, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2001-01-18 Online:2002-02-24 Published:2002-02-24

PDF (PC)

被引次数

18

摘要： 用量子化学AMI方法优化了1-苯基二苯并膦二磺化产物(PDBPDS)和三磺化三苯基膦(TPPTS)的几何构型.比较两种化合物的空间结构和电子结构发现,在氢甲酰化铑膦催化反应体系中,PDBPDS的配体性能优于TPPTS.首次研究了以PDBPDS为配体的铑膦催化剂对丙烯氢甲酰化反应的催化性能,考察了反应温度、压力、膦铑物质的量比和搅拌速度对催化活性和选择性的影响.结果表明,在2.0MPa,100℃,膦铑物质的量比为35,搅拌速度为500r/min及V(H2)/V(CO)=1/1的条件下,催化活性可达到2800g(丁醛)/[g(铑)·h],正异构产物物质的量比为12.3,在相同条件下与传统的三磺化三苯基膦(TPPTS)为配体的铑膦催化剂相比,催化活性和选择性提高了2倍.反应结束后,有机相和水相分离简单,有机相铑浓度仅为3.6×10-8mol/L,有效地解决了铑流失问题,表明PDBPDS是极具开发前景的新型水溶性配体.

关键词: 二磺化1-苯基二苯并膦(PDBPDS), 水溶性铑膦配合物, 氢甲酰化反应, 两相催化体系

Abstract: Structures of 1-phenyldibenzophosphole disulfonate(denoted as PDBPDS) and triphenylphosphorus trisulfonate(denoted as TPPTS) were optimized by using quantum chemical AM1 method. Both stereo and electronic structure show that PDBPDSacts as a better ligand than TPPTSin the Rh/Pcatalyst system of hydroformylation. The performance of the novel ligand PDBPDS in water soluble Rh complex, HRh(CO)(PDBPDS)3, was conducted in biphasic hydroformylation of propylene. The influences of reaction parameters such as reaction temperature, n (PDBPDS)/ n (Rh) and agitating speed on catalytic properties were investigated. The result shows that under the condition of 2.0 MPa, 100 ℃, n (PDBPDS) / n (Rh)=35, agitating speed 500 r/min and V (H2)/ V (Co)=1/1, TONis 2800 g(butyraldehyde)/ and the n (normal)/ n (iso) reaches 12.3, concentration of Rh in the organic phase is only 3.6×10-8 mol/L. Compared with the performance of TPPTSunder the same condition, both activity and selectivity are remarkably improved. Further, the catalyst can be easily separated from the reaction system.

Key words: PDBPDS, Water soluble phosphorus rhodium complex, Hydroformylation, Biphasic catalytic system

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