磁性纳米三苯基膦配体制备及其催化氢甲酰化反应  

Recyclable Magnetic Nano-triphenylphosphine Ligand:Preparation and Its Catalytic Property in Hydroformylation Reaction

作　　者：端木传嵩[1] 顾坚[2] 吴林林[2] 赵峰[2] 许兴友[1] 

机构地区：[1]淮阴工学院江苏省盐化工新材料工程实验室,江苏淮安223003 [2]淮阴工学院生命科学与化学工程学院,江苏淮安223003

出　　处：《精细化工》2015年第5期528-532,共5页Fine Chemicals

基　　金：国家自然科学基金(51103052);江苏省高校自然科学基金(11KJB430001);江苏省普通高校专业学位研究生科研实践计划项目(SJZZ14_0203)~~

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得磁性纳米三苯基膦配体,其结构通过红外光谱、元素分析以及热重分析进行了表征。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。在优化后的反应条件下,即苯乙烯1.25 m L,30 mg磁性纳米三苯基膦,1.8 mg Rh(OAc)2,12 m L无水四氢呋喃,3 MPa合成气VCO∶VH2=1∶1,纳米三苯基膦配体中的三苯基膦含量为0.21μmol/mg,该配体能够与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%的三苯基膦配体从纳米粒子表面脱落。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 the magnetic nano-triphenylphosphine was characterized by means of 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 to nanoparticles and sonication time. Under the optimized conditions, the triphenylphosphine content in the magnetic nano-triphenylphosphine ligand was 0.21 μmol/mg. The magnetic nano-triphenylphosphine 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 conditions with only 4. 8% of triphenylphosphine dropped off from the nanoparticle surface. The optimum reaction conditions of styrene hydroformylation were： 1.25 mL styrene, 30 mg nano- triphenylphosphine （0. 006 3 mmol TPP） ,1.8 mg Rh（ OAc）2,12 mL THF,3 MPa syngas （ Vco：VH2 = 1 ： 1 ） ,90 ℃, reaction time 9 h.

关 键 词：磁性纳米三苯基膦 氢甲酰化反应 多巴胺-三苯基膦衍生物 纳米氧化铁粒子 催化与分离提纯技术 

分 类 号：O643.36[理学—物理化学]