催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (4): 566-571.DOI: 10.1016/S1872-2067(10)60182-9

• 研究论文 • 上一篇    下一篇

阳离子表面活性剂存在下水/有机两相体系中双环戊二烯氢甲酰化

皮晓栋1, 周娅芬1,2, 周丽梅1,2, 袁茂林1, 李瑞祥1, 付海燕1, 陈华1   

  1. 1四川大学化学学院绿色化学与技术教育部重点实验室, 四川成都 610064; 2华西师范大学化学与化工学院, 四川南充 637002
  • 收稿日期:2010-10-08 修回日期:2011-01-05 出版日期:2011-04-18 发布日期:2014-08-30

Dicyclopentadiene Hydroformylation in an Aqueous/Organic Two Phase System in the Presence of a Cationic Surfactant

PI Xiaodong1, ZHOU Yafen1,2, ZHOU Limei1,2, YUAN Maolin1, LI Ruixiang1, FU Haiyan1,#, CHEN Hua1,*   

  1. 1Key Laboratory of Green Chemistry and Technology of Ministry of Education, Department of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China; 2College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, Sichuan, China
  • Received:2010-10-08 Revised:2011-01-05 Online:2011-04-18 Published:2014-08-30

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961

被引次数

15

摘要： 研究了在阳离子表面活性剂存在下水/有机两相中水溶性铑配合物 RhCl(CO)(TPPTS)2 (TPPTS: P(m-C6H4SO3Na)3) 催化双环戊二烯氢甲酰化反应, 考察了反应温度、催化剂浓度、不同水溶性膦配体 TPPTS 和 TPPDS (C6H5P(m-C6H4SO3Na)2), 以及表面活性剂结构对催化反应的影响. 结果表明, 配体 TPPTS 比 TPPDS 表现出更好的助催化效果; 阳离子表面活性剂 C16H33N(CH3)2CnH2n+1Br (n = 1, 8, 12, 16) 的加入可大大加速反应, 但加速作用随着其中 CnH2n+1Br (n = 1, 8, 12, 16) 链长的增加而减弱; 在阳离子表面活性剂 (0.05~5.00 mmol/L) 存在下, 双环戊二烯的转化率随表面活性剂浓度的增加先增加后降低. 含催化剂的水相循环使用 4 次后, 催化活性和区域选择性没有明显下降.

关键词: 水/有机两相体系, 双环戊二烯, 氢甲酰化, 铑, 表面活性剂

Abstract: Dicyclopentadiene (DCPD) hydroformylation catalyzed by the water soluble rhodium complex RhCl(CO)(TPPTS)2 (TPPTS: P(m-C6H4SO3Na)3) was studied in an aqueous/organic two phase system containing a cationic surfactant. The effects of various reaction parameters such as reaction temperature, catalyst concentration, water soluble phosphine TPPTS or TPPDS (C6H5P(m-C6H4SO3Na)2), and surfactant structure were examined. The catalytic activity was better with the ligand TPPTS than with TPPDS. The reaction was accelerated by the addition of the cationic surfactant C16H33N(CH3)2CnH2n+1Br (n = 1, 8, 12, 16) but the accelerating effect was attenuated with an increase of the n value. In the presence of the surfactant, the DCPD conversion increased initially and then decreased as the rhodium concentration increased in the range of 0.05–5.00 mmol/L. The catalyst containing aqueous phase was reused four times without significant decrease in activity and regioselectivity.

Key words: aqueous/organic two phase system, dicyclopentadiene, hydroformylation, rhodium, surfactant