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聚苯乙烯基微球固定化Pd-卟啉在Heck反应中的应用研究
Alternative TitleApplied Research of Polystyrene Microspheres Immobilized Pd-porphyrin in Heck Reactions
黄寅斌
Subtype硕士
Thesis Advisor刘会洲 ; 杨良嵘
2013-04-01
Degree Grantor中国科学院研究生院
Degree Discipline化学工程
KeywordHeck反应催化剂   pd卟啉   聚苯乙烯微球   非均相反应
AbstractHeck反应是指在碱性条件下钯催化的芳基或乙烯基卤代物和活性烯烃之间的偶联反应。该反应因底物适用性广,立体选择性高,反应条件温和,而逐渐发展为一种应用日益广泛的有机合成方法,为众多天然产物、生物活性物质、精细化学品及其中间体提供了有效且丰富的合成手段。Heck反应催化剂一直是Heck反应的研究热点。其中,均相Pd基催化剂因具有较高的Heck反应催化活性和选择性而成为首选。但是,均相Heck反应催化剂存在分离回收困难、容易失活和价格昂贵等问题,大大限制了其在工业上的广泛应用。 针对这些问题,本论文较系统地开展了负载型无磁和磁性聚苯乙烯Pd卟啉催化剂的制备、表征及Heck反应评价等方面的研究工作。主要取得了以下两个方面的研究结果: 首先,在80℃,无水环境,DMF作为溶剂的条件下,卟啉外围的-OH与聚苯乙烯表面的-CH2-Cl发生交联反应生成共价C-O-C键,从而实现卟啉在聚苯乙烯微球表面的固载;再通过Pd2+与聚苯乙烯微球表面的卟啉环的配位实现Pd的负载,最终得到平均粒径为64.45 μm,钯负载量为0.24 wt%的聚苯乙烯钯卟啉微球。将该微球用于Heck反应评价,结果表明:在碘苯衍生物与丙烯酸乙酯的Heck反应体系中,PS/Pd-MTP催化剂对不同的Heck反应体系表现出很高的催化活性(yeild:79.2-100%);Heck模型反应重复使用性能评价表明:PS/Pd-MTP催化剂对于Heck模型反应具有优异的重复使用性能,连续使用6次催化活性未见活性下降(yeild:94.3-99.8%)。通过与同领域的文献报道相比:PS/Pd-MTP催化剂对于Heck反应具有无溶剂使用,低催化剂用量,无Pd泄露,反应条件温和等特点。 其次,利用悬浮聚合法合成了磁性聚苯乙烯微球,对磁性聚苯乙烯表面进行氯甲基化,成功制备了氯甲基化的磁性聚苯乙烯微球;根据第二章摸索合成聚苯乙烯Pd卟啉微球的条件,成功制备出了平均粒径为35.19 μm,Pd负载量为0.38 wt%的磁性聚苯乙烯Pd卟啉微球,饱和磁化强度为10.9 emu/g。将该微球应用于Heck反应评价,结果表明:在碘苯衍生物与丙烯酸乙酯的Heck反应体系中,磁性PS/Pd-MTP催化剂对不同的Heck反应体系表现出很高的催化活性(yeild:82.7-100%);Heck模型反应重复使用性能评价表明: 磁性PS/Pd-MTP催化剂对于Heck模型反应具有优异的重复使用性能,连续使用10次催化活性未见活性下降(yeild:93.9-97.8%)。通过与同领域的文献报道相比:磁性PS/Pd-MTP催化剂对于Heck反应具有无溶剂使用,低催化剂用量,无Pd泄露,反应条件温和等优点外,还具有在磁场中易于分离的特点。
Other AbstractThe Heck Reactions are palladium-catalyzed C-C coupling reactions between aryl or vinyl halides and active olefin under alkaline conditions,which have gradually been developed into increasingly widespread organic synthesis method for the wide applicability to substrates, high stereoselectivity, mild reaction conditions; have provided effective and rich organic synthesis means for many natural products, biologically active substances, fine chemicals and their intermediates. Heck reaction catalyst has been the research core of the Heck reaction. Homogeneous Pd catalysts have became the first choice for the higher catalytic activity and the excellent selectivity. However, homogeneous Heck reactions’applications in industry have been limited due to their difficult separation and recovery, easy to inactivation and their expensive price. In this present work, the preparation, characterization and evaluation of Heck reaction research of PS/Pd-MTP and magnetic PS/Pd-MTP have been systematically studied. Firstly, At 80 °C, DMF, anhydrous environment, immobilized porphyrin on the surface of the polystyrene microspheres by forming a C-O-C covalent bond between -CH2-Cl on the surface of the polystyrene microspheres and the -OH on the MTP; Got the PS/Pd-MTP by coordinating Pd2+ to porphyrin ring on the surface of the polystyrene microspheres. At last The characterization results showed that the average particle diameter of PS/Pd-MTP was 64.45 μm, palladium loadings was 0.24 wt%. The PS/Pd-MTP was applied in the Heck reaction. The Evaluation results showed that: in Heck reaction between the iodobenzene derivative and ethyl acrylate, the PS/Pd-MTP catalyst showed excellent catalytic activity (yeild: 79.2-100%); In Heck model reaction between the iodobenzene and ethyl acrylate, the PS/Pd-MTP catalyst show great reusability. After using 6 batches, the catalytic activity did not decreased (yeild:94.3-99.8%). Compared to literatures in the Heck reaction catalysts field: PS/Pd-MTP catalyst have many advantages such as solvent-free, low amount of catalyst, no Pd-leaching, mild reaction conditions etc. Secondly, the PS-CH2-Cl was got by synthetizing the magnetic polystyrene microspheres the using suspension polymerization method and chloromethylating the surface of the magnetic polystyrene. According to the conditions(The second chapter), magnetic PS/Pd-MTP was prepared. The characterization results showed that the average particle diameter of magnetic PS/Pd-MTP was 35.19 μm, palladium loadings was 0.38 wt%, Saturation magnetization was 10.9 emu/g. The magnetic PS/Pd-MTP was applied in the Heck reaction. The Evaluation results showed that: in Heck reaction between the iodobenzene derivative and ethyl acrylate, the magnetic PS/Pd-MTP catalyst showed excellent catalytic activity (yeild: 82.7-100%); In Heck model reaction between the iodobenzene and ethyl acrylate, the magnetic PS/Pd-MTP catalyst show great reusability. After using 10 batches, the catalytic activity of magnetic PS/Pd-MTP did not decreased (yeild: 93.9-97.8%). Compared to literatures in the Heck reaction catalysts field: magnetic PS/Pd-MTP catalyst have many advantages such as solvent-free, low amount of catalyst, no Pd-leaching, mild reaction conditions etc. Besides the magnetic PS/Pd-MTP has the characteristics of easy separation in a magnetic field.
Pages97
Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/8366
Collection研究所(批量导入)
Recommended Citation
GB/T 7714
黄寅斌. 聚苯乙烯基微球固定化Pd-卟啉在Heck反应中的应用研究[D]. 中国科学院研究生院,2013.
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