高分子负载钯催化Suzuki反应的研究进展

高分子负载钯催化剂与均相催化剂相比易于分离、可重复使用,同时大多数高分子负载钯催化剂保留了较高的催化活性。高分子负载钯催化剂已成为Suzuki反应催化剂的研究热点之一。本文综述了近年来高分子负载钯络合物及钯纳米催化剂在Suzuki反应中的研究进展。     

负载型钯催化剂在Heck反应中的应用

比较了Heck反应中传统的催化剂在分离和回收方面的问题,介绍了负载型钯催化剂的优点,归纳了负载型钯催化剂按固相载体高分子、二氧化硅、活性炭、分子筛和金属氧化物等进行的分类,总结了各类负载型钯催化剂在Heck反应中的应用。认为目前还必须克服负载型催化剂易流失、成本高等问题。     

无配体负载钯催化Suzuki偶联反应的研究进展

金属钯催化的Suzuki偶联反应是碳一碳偶联反应中的最重要的反应之一。传统的均相催化体系具有很多的不足,如产物与催化剂不易分离、原料价格昂贵、催化剂不能重复使用等,而使用无配体负载钯的催化剂可有效地解决上述问题。综述了近些年来无配体材料负载钯催化Suzuki偶联反应的研究进展,载体包括碳材料、多孔分子筛、水滑石、高分子材料、金属氧化物、硅藻土、纤维素、磷灰石和氟硅胶等。     

含有联二萘结构手性负载催化剂用于不对称催化反应研究进展

不对称催化是获得单一光学活性化合物最好的方法之一,然而贵重的手性催化剂的分离与回收是一个难题,针对BINOL、BINAP这两类具有联二萘结构的手性负载催化剂近年的研究进行了总结,认为以结构可控的高分子为载体,发展从分子水平上设计高分子手性配体及催化剂的方法是可行的。     

多相铂催化剂在芳香族化合物加氢中的应用

介绍了负载型铂催化剂、高分子铂络合物催化剂和负载型含铂双金属催化剂等几种多相铂催化剂在芳香族化合物加氢中的应用及各自特点，展示这类催化剂在反应中具有良好的催化活性。     

低成本环状碳酸酯新工艺诞生

南开大学的科研人员将一种新型固体催化剂用于制备环状碳酸酯，大大简化了工艺流程，产品无需经过分离、纯化过程，纯度就可高达99％以上。这种高分子负载催化剂可做到一相反应、两相分离，大大降低了生产成本。这项环状碳酸酯新工艺目前已引起业界的极大关注。     

导电高分子负载贵金属燃料电池催化剂的研究进展

综述了近年来国内外聚苯胺(PANI)、聚吡咯(PPy)、聚噻吩(PTh)以及它们的一些衍生物或复合物等导电高分子负载贵金属复合催化剂在燃料电池中的研究进展。指出金属颗粒在具有多孔结构、高表面积、低电阻和高的稳定性的导电高分子材料中具有较好的分散性,导电高分子负载贵金属催化剂呈现出较高的催化活性和耐CO中毒性能,从而提高了催化效率。     

多孔壳聚糖微球/钯催化剂应用于水相Heck反应

以与壳聚糖具有一定相容性的水溶性高分子(聚乙二醇)为致孔剂,通过相转变法制得了多孔壳聚糖微球负载钯催化剂.利用扫描电镜、ICP-AES等对催化剂进行了表征.结果表明,所制备的壳聚糖基多孔微球具有高度开放的多孔结构,钯可有效的进入高分子微球的孔道中实现有效负载.该负载型催化剂能较好地催化丙烯酸丁酯与芳基碘系物的水相Hec...     

有机载体负载茂金属催化剂研究进展

综述了近年来天然高分子、聚合物等有机载体用于负载茂金属催化剂的研究现状,评述了有机载体型茂金属催化剂的特点、负载方式、负载化对催化烯烃聚合性能和聚合物性能的影响。分析表明,进一步提高有机载体型茂金属催化剂的活性、改善有机载体的形态和结构仍是值得探索的课题。     

茂金属烯烃聚合催化剂——Ⅴ.茂金属催化剂多相化研究

介绍了茂金属化合物及其他单活性中心催化剂负载于SiO_2、MgCl_2、沸石、高分子材料等多种不同的载体上合成载体催化剂的研究,以及茂金属催化剂用于烯烃聚合反应的特征。     

聚合物固载催化剂的研究进展

综述了近年来聚合物固载催化剂的研究进展。介绍的聚合物固载催化剂有6类，包括离子交换树脂催化剂、聚合物固载的相转移催化剂、聚合物固载的酸催化剂、聚合物固载的碱催化剂、聚合物固载的金属催化剂、聚合物固载的生物催化剂等。     

聚合物固载催化剂的研究进展

介绍聚合物固载催化剂有6类,包括离子交换树脂催化剂,聚合物固载的相转移催化剂,聚合物固载的酸催化剂,聚合物固载的碱催化剂,聚合物固载的金属催化剂,聚合物固载的生物催化剂等。综述了近年来聚合物固载催化剂的研究进展。     

Vanadium Complexes Based Polymer Supported Catalysts: A Brief Account of Research from Our Group

Solid supported catalysts can go a long way in developing catalyst based technology because of their high efficiency with recyclability and easy separation from the reaction mixture. Immobilizations of homogeneous catalysts through covalent bond with chloromethylated polystyrene cross-linked with divinylbenzene and develop them as environmentally safe heterogeneous catalysts for oxidation reaction have attracted attention in recent years. Recently, effort from our research laboratory was to synthesize new recyclable polymer-supported vanadium complexes based heterogeneous catalysts. Thus, chloromethylated polystyrene cross linked with 5% divinylbenzene was used as support to prepare variety of polymer supported vanadium catalysts. These catalysts have successfully been used for the oxidation and oxidative bromination of various organic substrates. Keeping in mind the industrial usage of these heterogeneous catalysts, the leaching and recycle ability of all polymer-supported catalysts have also been tested. Most catalysts are stable and do not leach during the catalytic reactions.     

Hydrogenation of Citral Over a Polymer Fibre Catalyst

A polymer-supported Pd catalyst was investigated in hydrogenation of citral (3,7-dimethyl-2,6-octadienal), which is a stereoisomer with an isolated and a conjugated double bond as well as a carbonyl group. The catalyst was a fibrous polymer-supported catalyst modified with functional groups and immobilized metals. A comparison of the polymer-supported catalyst with conventional catalysts was made.     

CATALYST PRODUCT SEPARATION TECHNIQUES IN HECK REACTION

The Heck reaction finds several applications in industry because it is one of the effective tools for the formation of a new C─C bond. In addition to the catalytic activity and selectivity, catalyst-product separation strategies are very important for the industrial application. There are various methods of interest ranging from conventional heterogeneous catalysts to heterogenization of homogeneous catalysts. The heterogeneous catalysts are classified into supported metal catalysts, zeolite-encapsulated catalysts, colloids-nanoparticles, and intercalated metal compounds. The homogeneous metal complexes catalysts are heterogenized using modified silica catalysts, polymer-supported catalysts, biphasic catalysts, supported liquid-phase catalysts, nonionic liquids solvents, perfluorinated solvents, and reusable homogeneous complexes. In general, heterogeneous catalysts are effective and stable at higher temperatures, which may be important for the activation of less reactive but less expensive chloroaryls substrates. However, the heterogeneous catalysts have a major drawback of poor selectivity toward Heck coupling products. The heterogenized metal complexes catalysts operate under relatively mild conditions as compared with heterogeneous catalysts, and so they can be applied to the production of pharmaceuticals and fine chemicals. Catalysis using supercritical solvents with catalyst separation techniques is promising for the development of green chemistry processes. Although the concepts described in this article have been reviewed mainly for Heck reactions, they should be applicable to a wide range of other chemical transformations (hydrogenation, carbonylation, hydroformylation, and so on) that, currently, are homogeneously catalyzed reactions.     

高分子负载铁催化剂的制备及其甲苯选择性氯化反应性能

通过金属铁离子与高分子载体进行螯合反应,制备高分子负载铁催化剂,用原子吸收光谱法测定催化剂中Fe3+含量,并利用傅里叶变换红外光谱仪、扫描电子显微镜、热重分析对制备的催化剂分子结构、微球形貌和热稳定性进行表征,并研究有机硫助催化剂的添加对高分子负载铁催化剂催化甲苯选择性氯化性能的影响。结果表明,铁离子与乙酰丙酮基的两个氧原子形成了六元螯合环的强相互作用,使Cl2分子更易极化,提高了催化反应速率;有机硫助催化剂不仅改变Cl—Cl键的强度,而且增大了亲电试剂的空间位阻,从而显著提高对位选择性和稳定性。1%(占甲苯的质量分数)高分子负载铁催化剂/0.05%(占甲苯的质量分数)有机硫助催化剂催化甲苯选择性氯化反应表现出最佳的催化性能,氯化反应2 h,甲苯转化率超过90%,对氯甲苯选择性55.74%,多氯甲苯质量分数低于1%。催化剂可重复使用。     

多相催化合成月桂氮酮的工艺研究

以硫酸法精制的工业溴代十二烷为原料,甲苯作溶剂,用KOH-KF/Al2O3作催化剂,采用分水操作,多相催化合成月桂氮酮,在反应温度90°C,反应时间3.5h的反应条件下,月桂氮酮收率达92.3%,纯度>98.5%。该方法工艺简单,操作方便,成本低,催化剂分离易,产品无需进一步精制,易于实现工业化。     

Anodic oxidation of benzyl alcohol to benzaldehyde in the presence of both redox mediator and polymer-supported phase-transfer catalyst

Using a polymer-supported phase-transfer catalyst (PTC) and a redox mediator, Cl^–/OCl^–, the anodic oxidation of benzyl alcohol was studied. The polymer support used in this study was synthesized by the method of suspension polymerization. The results revealed that on decreasing the crosslinking and increasing the content of chloromethylstyrene in the polymer support, the number of phase transfer active sites, tri-n-butylphosphine, in the polymer-supported PTC increased. The anodic oxidation of benzyl alcohol in the presence of the redox mediator, Cl^–/OCl^–, and polymer-supported PTC occurred in the reaction controlled region when the stirring rate exceeded 400 r.p.m. The results also revealed that the current efficiency for the anodic oxidation of benzyl alcohol was mainly affected by the characteristics and weight of the polymer-supported PTC, the pH, and the concentration of benzyl alcohol. However, the temperature affected the current efficiency only slightly.     

超临界流体技术制备生物可降解聚合物/药物纳米微粒研究进展

生物可降解聚合物/药物纳米微粒在药物靶向递送、有效成分封装和医疗诊断等领域具有突出的优势。超临界流体超细微粒制备技术具有绿色环保、制备方法种类多、粒径易调节和后续分离纯化容易等特点,得到了广泛的研究。为了得到满足使用要求的聚合物/药物纳米微粒,超临界流体制粒技术是有效的手段之一。论述了生物可降解聚合物纳米材料的特点和应用情况,简要介绍了超临界流体及特性,重点介绍了超临界溶液快速膨胀(RESS)、超临界抗溶剂沉淀(SAS)、超临界CO₂辅助雾化(SAA)和超临界流体乳液萃取(SFEE)的工艺特点、制备方法、基本原理和研究进展,并对超临界流体技术制备聚合物/药物纳米微粒的发展方向进行了展望。     

可溶聚合物支载催化剂

可溶聚合物支载催化剂是当今“绿色化学”研究的热点问题之一。本文介绍了近几年来可溶聚合物支载催化剂,包括可溶聚乙二醇、可溶聚丙烯酰胺和可溶非交联聚苯乙烯支载催化剂的研究情况及其在有机合成中的应用。