磁性纳米三苯基膦配体制备及其催化氢甲酰化反应研究

Recyclable Magnetic Nano-Triphenylphosphine Ligand: Preparation and its catalytic Property in Hydroformylation Reaction

摘要:

通过表面交换反应以多巴胺为偶联剂将三苯基膦担载到磁性纳米氧化铁表面制备出了磁性纳米三苯基膦配体,其结构通过红外吸收光谱、元素分析以及热重分析等方法进行了表征。初步考察了表面交换反应条件对三苯基膦在纳米粒子表面担载量的影响；提高多巴胺-三苯基膦衍生物与磁性纳米氧化铁粒子比例以及延长超声时间有助于提高三苯基膦的担载量。在优化后的制备条件下，纳米三苯基膦配体中的三苯基膦含量为0.21 umol/mg。该纳米三苯基膦配体能够与Rh(OAc)2一起催化苯乙烯的氢甲酰化反应并能重复使用4次，且仅有4.8%的三苯基瞵配体从纳米粒子表面脱落。

Abstract:

A recyclable magnetic triphenylphosphine ligand was prepared via a surface exchange reaction to load triphenylphosphine onto the surface of iron oxide nanoparticle with dopamine as a linker. The structure of magnetic nano-triphenylphosphine was characterized by IR, elemental analysis and TGA methods. The loading amount of triphenylphosphine on iron oxide nanoparticles could be elevated by increasing the ratio of dopamine-triphenylphosphine over nanoparticle and sonication time. Under the optimized condition, the triphenylphosphine content in the magnetic nano-triphenylphosphine ligand was 0.21 mol/mg. The magnetic nano-triphenylphsophine ligand could catalyze the hydroformylation reaction of styrene with Rh(OAc)2 as a Rh source and the in situ formed magnetic nano-triphenylphosphine-Rh catalyst could be recycled for 4 times under the optimum reaction condition with only 4.8% of triphenylphosphine dropped off from the nanoparticle surface. The optimum reaction condition of styrene hydroformylation was: 1.25 mL styrene, 30 mg nano-triphenylphosphine (0.0063 mmol TPP), 1.8 mg Rh(OAc)2, 12 mL THF, 3 MPa syngas (VCO:VH2 = 1:1), 90 °C, reaction time 9 h.