十一．欧洲专利数据库
1.Better sulphide catalysts through optimized active phase-support interaction Keywords:Active phase-support interaction; Excess stoichiometric; Hydrodesulfurization; Hydrotreating catalyst; CoMoS phase;FeMoS phase;
Temperature programmed reduction; Temperature program medsulphidation; XPS;EXAFS;XANES
Abstract:In this project, improved hydrotreating catalysts have been synthesized by varying the active phase-support interaction. This interaction has been changed by differing the calcining procedures and choice of catalyst precursors and carriers. The active phase consisted basically of molybdenum or tungsten disulphide, and Ni, Co, Cr or Fe as the promoter. Also phosphorus has been added as secondary promoter. As for the preparation of the catalysts, a new type of carrier, filamentary carbon supported by alumina, has been lysts have been developed and a better understanding of the fundamental characteristics of the catalysts has been acquired. Novel equipment has been developed. Two of its major features are a simple design and the possibility for the in situ measurement of physical parameters of the autoclave contents. For future development of the catalysts, a detailed kinetic analysis of their performance, and the application of in situ characterization techniques is of paramount importance. 2.On The State of the Co-MO-S Model Abstract
The present article will discuss the recent developments which have taken place with the “Co-Mo-S model”. Some new results will also be presented to elucidate some of the controversies which have existed in the literature. The Co-Mo-S model, which was originally based on M?ssbauer emission spectroscopy (MES) measurements, has now been confirmed and further developed by use of extended x-ray absorption fine structure (EXAFS), infrared spectroscopy (ir), x-ray photoelectron spectroscopy (XPS), high resolution and analytical electron microscopy (HREM and AEM), magnetic susceptibility and other methods. 3.Kinetic and Active Centre Studies on the Polymerization of Propylene using MgCl2 Supported Ziegler – Natta Catalysts and 1,3 Diether Donors
Keywords:active centre determination;MgCl2 supported catalysts;polypropylene (PP);Ziegler Natta polymerisation Abstract
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All polymerization experiments were carried out in a Büchi glass reactor capable of operating at propylene pressures of 1-7 atmospheres. Two types of MgCl2 supported catalysts with controlled morphology were studied, viz., catalyst systems containing either a 1,3 diether (Catalysts A and D), 9,9-bis (methoxymethyl) fluorene, or a simple diester (Catalysts B, C and E) such as diisobutylphthalate, used as reference systems. The kinetic behaviours of these catalysts were investigated for propylene polymerization. The 1,3-diether based systems proved to be excellent catalyst systems for propylene polymerization showing high polymerization activities and stable rate-time profiles and produced spherical polymer particles. Catalyst pre-treatment was found to play an important role in controlling the morphology of the final polymer. A tritiated alcohol radio-quenching technique was used to determine the concentrations active centres: values of 7.5 and 5.1 mol/mol % respectively were obtained for catalysts A and D and 3.5, 2.9 and 2.2 mol/mol % respectively were obtained for catalysts B, C and E. Catalysts A and D showed very high polymerization activities and also higher C0* values. All polymers produced were characterized by SEM, DSC, extraction and molecular weight determinations.
4.Kinetics of the esterification of acetic acid with 2-propanol: Impact of different acidic cation exchange resins on reaction mechanism Abstract
The kinetics of the esterification of acetic acid with the secondary alcohol, 2-propanol, catalyzed by the cation exchange resins, Dowex 50Wx8-400, Amberlite IR-120, and Amberlyst 15 has been studied at temperatures of 303, 323, and 343 K; acid to alcohol molar ratios of 0.5, 1, and 2; and catalyst loadings of 20, 40, and 60 g/L. The equilibrium constant was experimentally determined, and the reaction was found to be mildly exothermic. External and internal diffusion limitations were absent under the implemented experimental conditions. Systems catalyzed by gel-type resins (Dowex 50Wx8-400 and Amberlite IR-120) exhibit some similarities in their reaction kinetics. Increase in reaction temperature, acid to alcohol ratio, and catalyst loading is found to enhance reaction kinetics for the three catalysts. The pseudohomogeneous (PH), Eley Rideal (ER), Langmuir Hinshelwood (LH), modified Langmuir Hinshelwood (ML), and P?pken (PP) models were found to predict reaction kinetics with mean relative errors of less than 5.4%. However, the ML model was found to be better for predicting reaction kinetics in the systems catalyzed by gel-type resins, while the PP model was better for the system catalyzed by the macroreticular catalyst, Amberlyst 15.
5.Investigation of phthalocyanine catalysts for the aerobic synthesis of meso-substituted porphyrins
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Keywords:phthalocyanine catalysts;tetraphenylporphyrin synthesis; iron (II) phthalocyanine
Abstract:The aerobic oxidation process for the synthesis of porphyrins, previously performed using 5 mol % p-chloranil (TCQ), 5 mol % iron(II) phthalocyanine (FePc) and stoichiometric amounts of O2, has been refined using new phthalocyanine catalysts. Four phthalocyanine catalysts have been prepared, characterized by M?ssbauer spectroscopy and examined for efficacy in the high concentration (0.1 M) synthesis of tetraphenylporphyrin at room temperature. Each phthalocyanine has been identified to be a μ-oxo dimer. Two catalysts are soluble (the μ-oxo dimers [(t-butyl)4FePc]2O and [(n-C6H13O)4FePc]2O) and enable homogeneous reactions, while two are insoluble (the μ-oxo(1) and μ-oxo(2) dimers of FePc, (FePc)2O) and give heterogeneous reactions. These four phthalocyanine compounds provide efficient catalysis at the 0.3–1 mol % level using only 1 mol % quinone or hydroquinone (TCQ, DDQ, TCQH2 or DDQH2), affording ～25% yields of tetraphenylporphyrin in 60 min of oxidation. There are no discernible advantages of the homogeneous versus heterogeneous catalysts. The μ-oxo dimers are active, but FePc is inactive, at the 0.3 mol % level. The activity of the FePc sample at the 5 mol % level is attributed to residual μ-oxo dimer impurity. This aerobic oxidation process is superior to stoichiometric oxidation with TCQ or DDQ, and can be performed in the presence of BF3·O(Et)2, trifluoroacetic acid, or under neutral conditions. ? 1997 John Wiley & Sons, Ltd. 6. Characterization of Synthetic Iron Oxides and their Performance as Support for Au Catalysts.
Keywords:alcohols; gold;hydrogenation; nanostructures; supported catalysts Abstract
Gold(0) catalysts supported on ferric oxide are effective catalysts, and so far, the only heterogeneous ones known for the regioselective hydrogenation of ,β-unsaturated ketones to the corresponding ,β-unsaturated secondary alcohols. A set of ferric oxide samples, synthesized under strictly controlled conditions and thoroughly characterized (X-ray powder diffraction, M?ssbauer spectroscopy, micro-Raman spectroscopy, transmission electron microscopy, temperature-programmed reduction), were employed as supports of gold(0) catalysts for this reaction.
7. Ring-opening polymerization of ε-caprolactone using perfluoroalkanesulfonates and perfluoroalkanesulfonimides as organic catalysts
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Keywords:activation energy;caprolactone;kinetics (polym.);organic catalyst; polyester;recycling;ring-opening polymerization
Abstract:We examined ring-opening polymerizations (ROPs) of ε-caprolactone in toluene at 25–50 °C catalyzed by perfluoroalkanesulfonates and perfluoroalkanesulfonimides as organic catalysts. The ROPs proceeded quickly using these super Br?nsted acids as catalysts. We synthesized poly(ε-caprolactone)s (Mn = 4.8 × 10–13.5 × 10) with low polydispersity (Mw/Mn = 1.10–1.48). These strong Br?nsted acids catalyzed living polymerizations of ε-caprolactone. After polymerization, Nf2NH was recovered and reused. To survey solvents, CHCl3 and tetrahydrofuran (THF) were used instead of toluene as solvents for polymerization. When THF was used as a solvent, not only ε-caprolactone, but also THF was polymerized and incorporated into the polymer chain (incorporated THF ratio; 6–10%). We investigated the reaction kinetics and activation thermodynamics of the organic catalysts. The activation energy and the activation enthalpy values for the ROPs of ε-caprolactone using the catalyst having electron-withdrawing ligand were smaller, but the activation entropy value is more negative. Moreover, the ranked values of the activation enthalpy for the reaction well parallel the polarity of solvents. The ranked values of the activation free energies well parallel those of the times required for polymerization completion. Our findings indicate that the super Br?nsted acids are excellent catalysts for rapid ROP of ε-caprolactone: they are more active than N, N-dimethylaminopyridine (DMAP) or stannous (II)
2-ethylhexanoate [Sn(Oct)2]. ? 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
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十二．检索结论（文献综述）
近年来,多相化均相催化剂的研究,在有机合成、石油化工、精细化工等领域引起了广泛关注.和多相催化剂一样,负载化均相催化剂的性能也与制备技术有较大的关系.如在研究氯化钯、聚乙烯吡咯烷酮(PVP)和氧化铝所组成的双重负载催化剂时,虽然所用组分一样,比例相同,但由于负载顺序不同,所得催化剂的活性和重复使用性相差很大。
采用化学键连与溶胶-凝胶包容法制备锚链固定的多相催化剂。利用傅里叶变换红外光谱和核磁共振氢谱方法对催化剂及其前体进行表征。考察催化剂制备条件及环氧化反应条件对催化剂性能的影响,得到催化剂制备的优化条件及最佳环氧化反应条件。采用最佳条件下制备的催化剂催化环己烯的环氧化反应。将均相手性催化剂固定到有机聚合物、磁性的Fe3O4纳米颗粒、功能化修饰的分子筛等载体上;直接利用有机金属配合物中的阳离子和分子筛骨架中的阴离子相互作用实现多相化;采用金鸡纳生物碱等手性小分子为修饰剂和天然高分子为手性源制备多相催化剂。同时对不同途径
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制备的多相手性催化剂的结构特性、催化性能和立体选择性进行了评价。采用化学键联和溶胶-凝胶相结合的方法制备了带锚链固定的多相化铑膦络合物催化剂。利用FTIR,XPS,ICP及N2吸附对催化剂进行表征,揭示了催化剂内部结构与催化性能之间的关系。对催化剂的制备条件进行了优化,该催化剂用于1-己烯的氢甲酰化反应转化率达98.7％、选择性为99.5％、产物正构和异构的摩尔比为0.90。
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