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现代化工  2018, Vol. 38 Issue (7): 172-175    DOI: 10.16606/j.cnki.issn0253-4320.2018.07.039
  科研与开发 本期目录 | 过刊浏览 | 高级检索 |
铑催化剂在1-辛烯氢甲酰化反应中的应用
胡嵩霜, 郑明芳
中国石油化工股份有限公司北京北化院燕山分院, 北京 102500
Application of Rh-based catalyst in hydroformylation reaction of 1-octene
HU Song-shuang, ZHENG Ming-fang
Yanshan Branch, Sinopec Beijing Research Institute of Chemical Industry, Beijing 102500, China
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摘要 从铑膦络合物前体、配体和反应条件等方面考察了均相铑催化剂用于1-辛烯氢甲酰化反应的性质和规律,其中铑膦络合物前体包括三(三苯基膦)羰基氢化铑[RhH (CO)(PPh33]、三(三苯基膦)氯铑[RhCl (PPh33]和羰基乙酰丙酮(三苯基膦)铑[Rh (CO)(PPh3)(acac)],配体包括三苯基膦(TPP)和三苯基氧膦(TPPO)。实验结果表明,在2 MPa、90℃的实验条件下,RhH (CO)(PPh33与PPh3组合时的反应活性及选择性明显高于其他组合,且在反应压力为2 MPa时RhH (CO)(PPh33/TPP体系的最佳反应温度为90℃。当反应压力在1~4 MPa时,随着压力的增加,反应活性增加。当Rh浓度固定时,随着TPP用量的增加烯烃转化率略有增加,而正壬醛的选择性明显增加。通过31P核磁共振技术对反应前后催化剂进行表征,结果表明,温度越高,催化剂体系中的膦配体越易被氧化,影响催化活性。
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胡嵩霜
郑明芳
关键词:  铑催化剂  膦配体  1-辛烯  氢甲酰化    
Abstract: The hydroformylation of 1-octene over homogeneous Rh-catalyst is investigated in terms of rhodium phosphine complex precursors,ligand effect and reaction conditions,wherein the precursors include carbonyl tris(triphenylphosphine) rhodium(I) hydride (RhH(CO)(PPh3)3),chloro tris(triphenylphosphine) rhodium(I) (RhCl(PPh3)3) and rhodium (triphenylphosphine) carbonyl acetylacetonate (Rh(CO)(PPh3)(acac)),and the ligands include triphenylphosphine (TPP) and triphenylphosphine oxide (TPPO).The results show that the reaction activity and selectivity of RhH(CO)(PPh3)3/TPP are better than others at 2 MPa,90℃,and the optimum reaction temperature of RhH(CO)(PPh3)3/TPP is 90℃ at 2 MPa.When the reaction pressure is within 1-4 MPa,the increase of pressure will increase its reaction activity.The change of catalyst before and after reaction is characterized by means of 31P(1H)NMR spectroscopy.The characterization results suggest that the higher the temperature,the easier to be oxidized the phosphine ligands.
Key words:  rhodium-based catalyst    phosphine ligand    1-octene    hydroformylation
收稿日期:  2018-03-12      修回日期:  2018-05-07           出版日期:  2018-07-20
O643.3  
通讯作者:  胡嵩霜(1989-),女,博士,工程师,研究方向为α-烯烃技术开发与应用,通讯联系人,010-80344810,hussh8.bjhy@sinopec.com。    E-mail:  hussh8.bjhy@sinopec.com
引用本文:    
胡嵩霜, 郑明芳. 铑催化剂在1-辛烯氢甲酰化反应中的应用[J]. 现代化工, 2018, 38(7): 172-175.
HU Song-shuang, ZHENG Ming-fang. Application of Rh-based catalyst in hydroformylation reaction of 1-octene. Modern Chemical Industry, 2018, 38(7): 172-175.
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http://www.xdhg.com.cn/CN/10.16606/j.cnki.issn0253-4320.2018.07.039  或          http://www.xdhg.com.cn/CN/Y2018/V38/I7/172
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