水/有机两相体系中催化氧化反应的研究进展

论述了水／有机两相体系中催化氧化反应的一些最新进展。由于采用水溶性催化剂，使得水／有机两相体系中的催化反应具有催化剂与产物容易分离的优点。阐述了水溶性催化剂在催化氧化反应中的应用，列举了一些典型的水溶性配体、水溶性催化剂以及催化氧化反应实例。参考文献21篇。     

Performance of a biomimetic oxidation catalyst immobilized on silicon wafers: comparison with its gold congener

With the aim of extending the usefulness of an existing biomimetic catalytic system, cobalt porphyrin catalytic units with thiol linkers were heterogenized via chemical grafting to silicon wafers and utilized for the catalytic oxidation of hydroquinone to p-benzoquinone. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to analyze the morphology and composition of the heterogeneous catalyst. The results of the catalytic oxidation of hydroquinone obtained with porphyrins grafted on silicon were compared with those obtained earlier with the same catalyst in homogeneous phase and immobilized on gold. It was found that the catalysis could run over 400 h, without showing any sign of deactivation. The measured catalytic activity is at least 10 times higher than that measured under homogeneous conditions, but also 10 times lower than that observed with the catalytic unit immobilized on gold. The reasons of this discrepancy are discussed in term of substrate influence and overlayer organization. The silicon-immobilized catalyst has potential as an advanced functional material with applications in oxidative heterogeneous catalysis of organic reactions, as it combines long-term relatively high activity with low cost.     

Kinetics and mechanism of stereospecific polymerization of methyl methacrylate with VOCl3–AlEt2Cl catalyst system

Methyl methacrylate was polymerized at 40°C with VOCl₃–AlEt₂Cl catalyst system in n-hexane. The rate of polymerization was proportional to catalyst and monomer concentration at Al/V ratio of 2 and overall activation energy of 9.25 kcal/mole support a coordinate anionic mechanism of polymerization. The catalytic activity and stereospecificity of this catalyst system is discussed in comparison with that of VOCl₃–AlEt₃ catalyst system.     

钯系催化剂的氨中毒研究

 考察了CO常压气相偶联合成草酸酯反应体系中在不同氨含量下P\r\nd系催化剂活性随反应时间的变化．结果表明，随着氨含量的增加，催\r\n化剂活性降低的速率加快，氨含量不超过0．54％时，仅引起催化剂活\r\n性下降，但不会造成催化剂完全失活；当氨含量达1．16％时，催化剂\r\n活性随反应时间迅速下降，直至完全失活．同时，观测了催化剂氨中毒\r\n的不可逆性．利用XPS和TEM表征手段探讨了Pd系催化剂氨中毒机理，并\r\n分析了在工业生产条件下催化剂氨中毒不可逆性的原因．     

钯-膦-酸体系催化烯烃氢酯基化反应研究进展

烯烃氢酯基化反应是羰基合成领域的重要分支之一,长期以来一直备受关注。目前已发展了钯基、铑基、钴基、钌基等众多催化体系,其中钯-膦-酸催化体系因具有反应条件温和、底物普适性良好、催化性能优异等优点而得到最广泛、最深入的研究。因此,我们对均相、非均相的钯-膦-酸催化体系在烯烃氢酯基化反应中的研究应用进行了简要综述,并对催化机理、催化剂组成和性能进行讨论,最后指出稳定性高、可回收性好的非均相钯-膦-酸催化体系将是该领域的研究重点。     

Pd(OAc)_2/HQ/FePc、Pd(OAc)_2/FePc 催化烯烃氧化合成酮的研究

考察了在乙腈酸性水溶液中Ｐｄ（ＯＡｃ）２／氢醌（ＨＱ）／酞青铁（ＦｅＰｃ）和Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对环己烯、环戊烯、苯乙烯、正癸烯氧化合成相应酮的催化活性．实验结果表明，两类催化体系对环戊烯的酮基化均呈现出较高的催化活性，环戊酮收率可达９８％．在其它烯烃的氧化反应中，三元催化体系Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ的催化活性高于二元的Ｐｄ（ＯＡｃ）２／ＦｅＰｃ．这表明，在Ｗａｃｋｅｒ类催化体系中，电子传递体的作用是很重要的．对催化体系中各组分的作用进行了讨论，并给出了可能的催化作用机理．     

不对称茂金属[Me~2C(Cp)(Ind)]ZrCl~2催化剂制备支化聚乙烯的 研究

本文报道以[Me~2C(Cp)(Ind)]ZrCl~2为主催化剂,MAO为助催化剂,仅以乙烯为单体制备支化聚乙烯的结果。     

Dual Catalysis Sees the Light: Combining Photoredox with Organo‐, Acid,and Transition‐Metal Catalysis

The photoredox activation of organic substrates with visible light is a powerful methodology that generates reactive radical species under very mild conditions. When combined with another catalytic process in a dual catalytic system, novel, visible‐light‐promoted transformations have been realized that do not proceed using either catalyst in isolation. In this minireview, the state of the art in organic reactions mediated by dual catalytic systems merging photoredox activation with organo‐, acid or metal catalysis is discussed.     

生物油脂新型环氧化过程及机理研究

以金属有机化合物甲基三氧化铼(MTO)为催化剂, 双氧水为氧化剂新型化学方法合成环氧大豆油. 详细考察了催化剂在双氧水、溶剂和助剂等因素下的催化性能. 研究了该催化体系在其他油脂环氧化中的应用, 环氧产物的选择性在99%以上. 采用红外光谱法(IR)对产品进行表征. 通过紫外-可见分光光度法(UV-Vis)对催化剂的研究, 发现催化剂(MTO)在催化环氧化过程中形成催化中间体, 且催化活性很高. 对催化剂和双氧水相互作用机理及新型环氧化反应的机理进行了初步研究.     

Influence of H2O on alternating copolymerization with the EtnAlCl3-n-VOCl3 catalyst system

The effect of the catalytic amount of H₂O was investigated with the Et_nAlCl_3-n-VOCl₃ catalyst system on the alternating copolymerization of acrylic monomers with diolefins and styrene. The presence of the catalytic amount of H₂O produced an improvement in the yield and in the molecular weight as well as the structure of copolymer with the Et_nAlCl_3-n-VOCl₃ catalyst system. The efficiency of the aluminum components in the Et_nAlCl_3-n-VOCl₃ system appears with AlEt₃ and especially with Et_1.5AlCl_1.5. The catalytic activity was found to depend upon the H₂O Et_nAlCl_3-n molar ratio and was also affected by the order of mixing of the catalyst components and the monomers. Effective catalyst could be prepared when the catalyst components (except VOCl₃) were premixed without presence of monomers. The possible catalytic behavior of H₂O was discussed.     

重油催化裂化装置提升管内反应历程研究

利用自行研制的工业提升管在线取样系统对胜利石油化工总厂重油催化裂化装置提升管中下部进行在线取样，将取得的液体和催化剂榈进行处理分析，从而得到了重油催化装置提升管反应器中下部液体产品分布、催化剂活性、碳含量和焦炭H／C的变化规律。认为重油催化裂化的主要反应发生在提升管的中下部区域，并对提升管油剂混合处的渣油雾化、汽化和油剂接触状况进行了讨论。     

A pH-responsive TiO2-based Pickering emulsion system for in situ catalyst recycling

Through tuning the surface wettability of interfacially active TiO₂ particles, a pH-responsive Pickering emulsion system is formed, as in situ separation and recycling of the nano-catalysts system.     

Tetracarbonyl cobaltate ion supported on anion exchangers as a new heterogenized homogeneous catalyst: synthesis of acids and esters from organic halides

Catalysts consisting of tetracarbonyl cobaltate anion supported on commercially available anion exchange resins are readily prepared. Carbonylation of organic halides using this heterogenized catalyst leads either to acids or esters depending on the conditions. Some features of this catalytic system and the possible reaction mechanism are discussed.     

相转移催化合成增塑剂BBP和水杨醛的研究

相转移催化合成增塑剂ＢＢＰ和水杨醛的研究郭锡坤，高文华，曾东宇（汕头大学化学系，汕头５１５０６３）关键词相转移催化，季铵盐，聚乙二醇，邻苯二甲酸丁苄酯，水杨醛，增塑剂邻苯二甲酸丁苄酯（增塑剂ＢＢＰ）是一种优良的增塑剂．邻羟基苯甲醛（水杨醛）不仅是重要...     

Cross-linked polymer supported palladium catalyzed carbonylative Sonogashira coupling reaction in water

A cross-linked polymer-supported ionic liquid immobilized palladium catalyst, which is prepared by reaction of the Pd(OAc)₂ with copolymer of 3-butyl-1-vinylimidazolium iodide and divinylbenzene, was well characterized and employed as an effective heterogeneous catalyst for carbonylative Sonogashira coupling reaction of aryl iodides with terminal alkynes in water, affording the corresponding α,β-alkynyl ketones in good to excellent yields. The catalytic system not only solves the basic problem of homogeneous palladium catalyst recovery and reuse but also avoids the use of toxic phosphine ligands. The stability of supported palladium was also discussed.     

铜基催化剂用于一氧化碳催化消除研究进展

催化消除CO主要包括CO的完全氧化(CO-COOX)和优先氧化(CO-PROX).首先,结合本课题组的相关研究,按照催化剂体系介绍了Cu基催化剂在CO-COOX中的活性物种和组分之间的相互作用.其次,对用于富氢气氛下CO-PROX的Cu基催化剂进行了系统的分类总结,重点阐述了CuO-CeO2催化剂的制备方法、助剂改性、载体调变以及过渡金属离子掺杂(CuO/Ce1-xMxO2)、反相结构(CeO2/CuO)等方面对CO-PROX催化性能的影响.最后,总结了Cu基催化剂在CO-PROX中存在的问题,并展望了未来的研究趋势.     

对在乙丙共聚反应中添加活化剂时活化机理的探讨

本文研究了对-甲苯磺酰氯、偶氮苯和四氢呋喃三种添加剂。对乙丙共聚反应的活化作用,实验结果表明,偶氮苯的活化作用最显著,能提高催化效率10倍左右,对-甲苯磺酰氯提高3-6倍,四氢呋喃提高1-2倍。 本文对活化机理作了较详细的探讨,讨论了各种活化剂对聚合反应的影响、活化剂对聚合反应动力学行为的影响,并研究了活化剂与催化剂各组分之间的反应。对上述三种活化剂提出了两种可能的活化途径。对-甲苯磺酰氯和偶氮苯的作用主要是使失去活性的V²⁺氧化成有活性的V³⁺化合物,从而增加了活性中心浓度使催化效率提高。而四氢呋喃主要是使V³⁺化合物稳定而延长活性寿命来提高催化效率。最后还提出了前两种活化剂氧化V²⁺化合物可能的反应历程。     

Linear Alpha-Olefins by Catalytic Oligomerization of Ethylene

This paper describes a new catalytic process for linear alpha-olefins by oligomerization of ethylene using a soluble alkyl aluminum chloride-titanium tetrachloride catalyst. Important catalytic and polymerization variables, such as catalyst activity, selectivity to linear products, and molecular weight, are discussed. An ionic mechanism is proposed to explain the unusual features of this new process.     

环烷酸钴-氯二异丁基铝催化体系相态的研究

研究了Co(naph) 2 Al(i Bu) 2 Cl催化体系的相态 .通过Tyndall效应、电镜观察和超过滤实验 ,证明了Co(naph) 2 Al(i Bu) 2 Cl催化体系在溶有丁二烯的苯溶剂中以纳米级小颗粒分散 ,在较佳配比时 ,粒径在 1～10 0nm之间 ,为胶体催化剂 ,属于高度分散的多相催化体系 .催化剂的活性位位于胶粒表面 ,催化剂颗粒是无定形的 .以较佳配比得到的催化剂颗粒较小、分布均匀 ,催化丁二烯聚合反应活性高 .归纳出胶体催化剂的制备特点为外观类似于均相催化体系 ,但是制备方法 (各组分配比、加入顺序、陈化等 )对催化活性有明显的影响 .并给出将胶体催化动力学作均相动力学近似的条件 ,在聚合反应初期 ,且单体浓度比烷基铝以及其他填加物浓度大 2～ 3数量级     

XiDehalogenation of Aryl Halides Catalyzed by MontK10 Immobilized PVP-Pd-Sn Catalyst in Aqueous System

Catalytic dehalogenation of organic halides is of great value to the organic synthesis and for the preventing of environmental pollution. Although, in recent years, there are many reports describing dehalogenation of organic halides in the literature1,2,3, most of them were carried out in the organic system,only few examples4,5 of dehalogenation were carried out in aqueous system. The toxic aryl halides may contaminate and harm human being seriously through food chain. Therefore, it is of utmo…