硅胶键合膦的制备及其对铑络合物催化1-辛烯氢甲酰化反应的影响

doi:10.3866/PKU.WHXB201502063

物理化学学报 >> 2015, Vol. 31 >> Issue (4): 738-742.doi: 10.3866/PKU.WHXB201502063

硅胶键合膦的制备及其对铑络合物催化1-辛烯氢甲酰化反应的影响

张晓亚, 郑从野, 郑学丽, 付海燕, 袁茂林, 李瑞祥, 陈华

四川大学化学学院有机金属络合催化研究所, 绿色化学与技术教育部重点实验室, 成都610064

收稿日期:2014-12-15 修回日期:2015-02-05 发布日期:2015-04-03
通讯作者: 袁茂林 E-mail:cdscyml@sina.com.cn
基金资助:
中国石油天然气股份有限公司石油化工研究所(2011B-2606)和四川大学青年教师科研启动基金(2011SCU11084)资助

Preparation of Silica-Bonded Phosphine and Its Influence on 1-Octene Hydroformylation Catalyzed by Rhodium Complex

ZHANG Xiao-Ya, ZHENG Cong-Ye, ZHENG Xue-Li, FU Hai-Yan, YUAN Mao-Lin, LI Rui-Xiang, CHEN Hua

Key Laboratory of Green Chemistry and Technology of the Ministry of Education, Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China

Received:2014-12-15 Revised:2015-02-05 Published:2015-04-03
Contact: YUAN Mao-Lin E-mail:cdscyml@sina.com.cn
Supported by:
The project was supported by the Petrochemical Research Institute of China National Petroleum Corporation, China (2011B-2606) and Sichuan University Scientific Research Foundation for Young Teachers, China (2011SCU11084).

摘要/Abstract

摘要：

以硅胶为载体, 采用键合接枝法将2-(二苯膦基)乙基三乙氧基硅烷(DPPES)共价键合于硅胶表面, 制备了性能优良的硅胶键合型膦配体(以SiO₂(PPh₂)表示). 以SiO₂(PPh₂)为配体, Rh(acac)(CO)₂ (acac:乙酰丙酮)为催化前体, 负载铑膦络合物催化剂(SiO₂(PPh₂)/Rh)在1-辛烯氢甲酰化反应中原位生成. 对生成的负载型催化剂和硅胶键合型膦配体进行了傅里叶变换红外(FTIR)光谱表征, 考察了膦/铑摩尔浓度比([P]/[Rh])、温度等因素对铑催化的长链1-辛烯氢甲酰化反应的影响. 结果表明, 膦/铑摩尔浓度比的增加能显著提高反应的成醛选择性, 降低铑的流失. 在[P]/[Rh]=12、363 K、2.0 MPa、1.5 h 的温和反应条件下, 1-辛烯转化率和成醛选择性分别可达98.4%和95.3%, 其催化活性与DPPES或三苯基膦(TPP)作配体时的均相铑催化相近. 催化剂循环4 次后, 反应活性无明显下降, 1-辛烯转化率均在97.0%左右, 经电感耦合等离子体原子发射光谱(ICP-AES)检测,有机相中铑流失低于0.1%.

关键词: 硅胶, 2-(二苯膦基)乙基三乙氧基硅烷, 1-辛烯, 氢甲酰化, 成醛选择性, 铑络合物, 催化循环

Abstract:

Using silica as a support, 2-(diphenylphosphino)ethyltriethoxysilane (DPPES) was anchored on silica surface by a grafting method to produce a bonded phosphine (denoted as SiO₂(PPh₂)), which displays excellent performance. The supported SiO₂(PPh₂)/Rh catalyst was formed in situ in 1-octene hydroformylation with SiO₂(PPh₂) as ligand and Rh(acac)(CO)₂ as precursor (acac: acetylacetone). SiO₂(PPh₂) and SiO₂(PPh₂)/ Rh were characterized by Fourier transform infrared (FTIR) spectroscopy. The effects of the ratio of phosphine to rhodium ([P]/[Rh]) and reaction temperature on 1-octene hydroformylation were investigated. Results show that an increase of the ratio of phosphine to rhodium can greatly improve the selectivity for aldehydes and decrease the rhodium leaching in organic phase. Under the moderate conditions: [P]/[Rh]=12, 363 K, 2 MPa, and 1.5 h, the conversion of 1-octene and the selectivity for aldehydes were 98.4% and 95.3%, respectively. The catalytic activity could compare with homogeneous catalysis with DPPES or triphenylphosphine (TPP) as ligand. The reaction activity was clearly unchanged after the SiO₂(PPh₂)/Rh catalyst was reused four times, with the conversion of 1-octene remaining at 97.0%, the rhodium content leaching in organic phase detected by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) was less than 0.1%.

Key words: Silica, 2-(diphenylphosphino)ethyltriethoxysilane, 1-Octene, Hydroformylation, Selectivity for aldehyde, Rhodium complex, Catalyst recycle

张晓亚, 郑从野, 郑学丽, 付海燕, 袁茂林, 李瑞祥, 陈华. 硅胶键合膦的制备及其对铑络合物催化1-辛烯氢甲酰化反应的影响[J]. 物理化学学报, 2015, 31(4), 738-742. doi: 10.3866/PKU.WHXB201502063

ZHANG Xiao-Ya, ZHENG Cong-Ye, ZHENG Xue-Li, FU Hai-Yan, YUAN Mao-Lin, LI Rui-Xiang, CHEN Hua. Preparation of Silica-Bonded Phosphine and Its Influence on 1-Octene Hydroformylation Catalyzed by Rhodium Complex[J]. Acta Phys. -Chim. Sin. 2015, 31(4), 738-742. doi: 10.3866/PKU.WHXB201502063

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201502063

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I4/738

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硅胶键合膦的制备及其对铑络合物催化1-辛烯氢甲酰化反应的影响

Preparation of Silica-Bonded Phosphine and Its Influence on 1-Octene Hydroformylation Catalyzed by Rhodium Complex

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