Versatile Friedel-Crafts-type alkylation of benzene derivatives using a molybdenum complex/ortho-chloranil catalytic system

A variety of molybdenum complexes catalyze Friedel-Crafts-type alkylation reactions of benzene derivatives with alkenes and alcohols in the presence of an organic oxidant, o-chloranil. The utilization of [Mo(CO)(6)] and two equivalents of o-chloranil catalytically furnished the hydroarylation product of norbornene with p-xylene at 80 degrees C, whereas [Cr(CO)(6)] and [W(CO)(6)] failed to catalyze the same reaction, thus indicating the importance of the molybdenum source. The best results were obtained when a molybdenum(II) complex [CpMoCl(CO)(3)] (Cp=cyclopentadienyl) was used as a precatalyst. The hydroarylation reactions also took place with styrenes, cyclohexenes, and 1-hexene as olefin substrates. The electrophilic-substitution mechanism was proposed on the basis of the ortho/para selectivities and the Markovnikov selectivities observed for the hydroarylation products. Our hypothesis was further corroborated by the fact that in the presence of the [CpMoCl(CO)(3)]/o-chloranil catalytic system, secondary, benzylic, or allylic alcohols participated in the alkylation of benzenes with similar selectivities.     

Nd(naph)3-Al(i-Bu)3体系催化丙烯酸乙酯及丙烯酸亚丁酯聚合

丙烯酸酯类极性单体的聚合反应通常采用自由基型引发剂。过渡金属化合物与烷酸铝所组成的配位催化剂对这类极性单体的催化聚合迄今仍处于研究阶段。我们在稀土催化环氧烷烃聚合的基础上曾研究了稀土钕的磷酸盐体系催化甲基丙烯酸甲酯、正丁酯的聚合。本文研究了环烷酸钕体系催化丙烯酸乙酯及丙烯酸正丁酯的聚合特征。     

Photocatalytic reduction of carbon dioxide to methanol by Cu2O/SiC nanocrystallite under visible light irradiation

The Cu2O/SiC photocatalyst was obtained from SiC nanoparticles (NPs) modified by Cu2O. Their photocatalytic activities for reducing CO2 to CH3OH under visible light irradiation have been investigated. The results indicated that besides a small quantity of 6H-SiC, SiC NPs mainly consisted of 3C-SiC. The band gaps of SiC and Cu2O were estimated to be about 1.95 and 2.23 eV from UV-Vis spectra, respectively. The Cu2O modification can enhance the photocatalytic performance of SiC NPs, and the largest yields of methanol on SiC, Cu2O and Cu2O/SiC photocatalysts under visible light irradiation were 153, 104 and 191μmol/g, respectively.     

Synthesis of polyolefin composition in the presence of supported catalysts

Polyolefins are basic materials in the plastics. Their application is limited by their low thermostability, adhesion, hardness and other physico-mechanical properties. The following treatments are known to improve and modify polyolefin properties: the incorporation of inorganic or organic fillers with a greater hardness and rigidity into the polyolefin matrix, the grafting of functional groups to polyolefins, and crosslinking with the formation of a network structure in the polyolefin matrix. In the case of polymers and inorganic materials, the activation of their surface by the functionalizing and fixing of transition metals allows one to perform polymerization of monomers on a surface to obtain a polymer–polymer composites and a highly filled polymer–inorganic composites.     

Novel polypropene materials derived from vinylidene-terminated oligopropenes

Metallocene-based homogeneous Ziegler–Natta catalysts produce mono-olefin-terminated oligopropenes with narrow molecular weight distributions, controlled stereoregularities, and molecular weights ranging from 100 to 30,000 g/mole in high yield slurry and solution processes. Steric and molecular weight control are influenced by metallocene structures, and by polymerization conditions such as temperature and propene concentration. Predominantly mono-vinylidene-terminated oligopropenes are attractive intermediates, and feedstock for the synthesis of a variety of polypropylene materials, including blends, block and graft copolymers. The key step is the chain end functionalization of the vinylideneterminated oligopropenes via double bond conversion reactions, followed by the controlled synthesis of polypropylene block and graft copolymers. In melt and solution processes the olefinic end groups have been converted into a variety of polar functional groups, e.g. hydroxy, carboxy, succinic anhydride, thiol and acrylic groups. The thiol-terminated oligopropenes are chain transfer agents in radical methylmethacrylate polymerization with chain transfer constant measured to be 0.2. Acrylic monomers and styrene are grown onto the thiol end group via a chain transfer reaction, thus producing a family of block copolymers, e.g. poly(propene-b-methylmethacrylate) and poly(propene-b-styrene). As demonstrated by SEM fracture surface analysis, the poly(propene-b-styrene) block copolymers are efficient dispersing agents for compatibilizing polystyrene/polypropene (70/30) blends. Homo- and copolymerization of acrylic oligopropene macromonomers yield novel classes of graft copolymers with pendant isotactic or atactic oligopropene chains. Hydroxy-terminated oligopropenes are useful initiators in caprolactone polymerization to form poly(propene-b-caprolactone) block copolymers. IR spectroscopic studies demonstrate that succinic anhydride-terminated oligopropenes, obtained by ene-type addition of maleic anhydride to the olefinic oligopropene end group, react with oligomeric diamine-terminated polyamide-6,6 in the melt to yield polypropene-b-polyamide-6,6-b-polypropene triblock copolymers.     

Comonomer effects with high-activity titanium- and vanadium-based catalysts for ethylene polymerization

High-activity titanium- and vanadium-based catalysts for ethylene polymerization frequently show an increase in reaction rate in the presence of an α-olefin. The magnitude of this increase depends on the specific α-olefin. The results show propylene > 1-butene > 1-hexene in increasing initial reaction rates. Addition of certain electron-donor compounds to these catalysts can lower the magnitude of the comonomer effect and, in some cases, totally eliminate such an effect. Among the classes of electron-donor compounds examined were ether-alcohols, ether-esters, amino-alcohols, alkoxysilanes, siloxanes, and phosphine oxides. Reaction kinetics show that the presence of a comonomer can influence the kinetic order of the reaction. These results can be interpreted using a mechanistic model involving two vacant coordination positions at the active sites. In this model electron donors and comonomers are viewed as Lewis-base ligands which influence features of chain propagation and chain termination. As Lewis-base ligands, the comonomers can also increase the number of active sites available for polymerization. Catalyst deactivation following the initial comonomer rate increase is believed to be caused by reaction with the Lewis bases (α-olefin included) in the system and by possible reduction in the oxidation state of the metal centers. The most acidic metal centers activated by the comonomer are most reactive to Lewis bases and deactivate most rapidly. Veratrole (1,2-dimethoxybenzene) can be employed as a probe for estimating the number of bis-vacant coordination sites in vanadium-based catalysts. Addition of low levels of veratrole led to significant deactivation of the vanadium-based catalyst. © 1993 John Wiley & Sons, Inc.     

Au/N-Ti-HMS的制备及其催化丙烯直接环氧化反应的研究

以十二胺为模板剂合成了一系列不同Ti含量的介孔分子筛Ti-HMS,并通过高温氨处理对其进行高温改性,在分子筛表面和骨架中引入碱性N原子.分别以改性前后的Ti-HMS为载体使用沉积沉淀法制得纳米金催化剂,并考察氢气、氧气共存条件下催化丙烯气相直接环氧化的催化性能.通过氮气等温吸附-脱附、X射线衍射(XRD)、傅里叶变换红...     

一氧化碳在高温超导体型的Ba2-xSrxYCu3O7-a上的催化氧化

用粉末XRD法、EXAFS法,激光喇曼散射法、热重法和高真空质谱TPD法研究了超导体型氧化还原催化剂Ba_(2-x)Sr_xYCu_3O_(7-α)(x=0,0.25, 0.50, 0.75, 1.00)的物理化学性质, 并用常压连续流动法测定了它们的CO催化氧化活性, 得到了催化剂氧化反应活性大小与催化剂的可失氧量(即晶胞中O_I 位置上的氧量)之间存在着线性关系的结论.     

Ti-Si composite oxide-supported cobalt catalysts for CO2 hydrogenation

In the present work, different silica-based supported cobalt (Co) catalysts were synthesized and used for CO2 hydrogenation for methanation. Different supports, such as SSP, MCM-41, TiSSP and TiMCM were used to prepare Co catalysts with 20 wt% Co loading. The supports and catalysts were characterized by means of N2 physisorption, XRD, SEM/EDX, XPS, TPR and CO chemisorption. It is found that after calcination of catalysts, Ti is present in the form of anatase. The introduction of Ti plays important roles in the properties of Co catalysts by:(i) facilitating the reduction of Co oxides species which are strongly interacted with support, (ii) preventing the formation of silicate compounds, and (iii) inhibiting the RWGS reaction. Based on CO2 hydrogenation, the CoTiMCM catalyst exhibites the highest activity and stability.