中华医学超声杂志

应用化学 ›› 1993, Vol. 0 ›› Issue (4): 13-17.

• 研究论文 • 上一篇    下一篇

SiO2负载的磺化三苯膦铑配合物催化高碳烯氢甲酰化

袁友珠, 陈鸿博, 蔡启瑞   

  1. 厦门大学化学系 361005 厦门
  • 收稿日期:1992-08-26 修回日期:1993-04-12 出版日期:1993-08-10 发布日期:1993-08-10
  • 基金资助:
    中国博士后基金;福建省自然科学基金

SiO2 SUPPORTED SULFONATED-TRIPHENYLPHOSPHINE-RHODIUM COMPLEXES CATALYZED HIGHER OLEFINS HYDROFORMYLATION

Yuan Youzhu, Chen Hongbo, Cai Qirui   

  1. Department of Chemistry, Xiamen University, 361005 Xiamen
  • Received:1992-08-26 Revised:1993-04-12 Published:1993-08-10 Online:1993-08-10

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摘要： 本文将水溶性磺化三苯基膦铑配合物催化剂负载在SiO2表面使其复相化,考察不同制备方法制得催化剂的性能及对反应活性和选择性的影响。这种负载化水溶性Wilkinson催化剂比表面积较大,可在适当过量配体存在下保持较高的催化活性;当液态高碳烯烃十一烯酸甲酯和1-己烯在固定床加压流动态反应器中连续进行氢甲酰化催化反应时,产物醛的选择性大于95%;正异醛比(n/i值)随P/Rh摩尔比的提高而提高P/Rh=15,产物中正构醛大于或接近80%(n/i为4)。P/Rh>15后,配体增多几乎不再提高产物n/i值,而影响反应速度。

关键词: 负载型催化剂, 磺化三苯基膦铑配合物, 氢甲酰化

Abstract: The catalytic species,water-soluble sulfonated-triphenylphosphine-rhodium complexes have been supported on SiO2 surface to form heterogenized-homogeneous catalysts denoted supported aque ous phase catalysts (SAPC). The SAPC possesses high catalytic activities even in the presence of excessive phosphine ligand owing to its high surface area. Hydroformylation of methyl 10-undecenoate and 1-hexene are easily carried out in an autoclave or fixed bed reactor over SAPC. With fixed bed reactor,aldehyde selectivities of up to 95% can be achieved in 4.0 MPa of CO/H2 (1/1, V/V) at 100℃; and the ratios of normal to isomcr aldehyde (n/i) were found to be increased with the increase of P/Rh ratios. It is also found that the reaction rate decreased and the n/i ratios of aldehydes were almost unchanged,when P/Rh ratios were over 15.

Key words: supported catalyst, sulfonated-triphenylphosphine rhodium complex, hydroformylation

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