超临界条件下碳酸乙烯酯的均相催化合成

合成了几种四齿 Schiff碱铝配合物 ,并用其在超临界条件下均相催化二氧化碳和环氧乙烷反应合成碳酸乙烯酯 .其中 ,以轴向为乙氧基链的 Schiff碱铝配合物的催化活性最高 .在一定条件下 ,由于环氧乙烷与超临界二氧化碳具有混溶性 ,使得环加成反应在超临界条件下比非临界条件下进行得更快 .反应温度对催化活性有很大影响 .碱性配体如 1 -甲基咪唑的存在能有效地提高这些铝配合物的催化性能 .同时 ,基于低温下的一些光谱数据 ,提出了可能的反应机理 .

均相催化法合成甲基丙烯酸丁酯

本文报导了以钛酸丁酯作催化剂,在均相条件下,由甲基丙烯酸甲酯与正丁醇进行酯交换反应合成甲基丙烯酸丁酯的新工艺。该法具有条件温和、操作简便、节约能源、产率高、质量好等优点。

Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller（BET）surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.

Synthesis of a Novel Solid Acid with both Sulfonic and Carbonyl Acid Groups and Its Catalytic Activities in Acetalization

The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.

Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

Catalytic synthesis of perfluorolyethers

Perfluorolyether is characterized by highly chemical inertness, oxidative stability, anticorrosion as well as radiation resistance. It can be used as lubricant especially in harsh environmental conditions. In this work, hexafluoropylene oxide was catalytically polymerized at low temperature using the methods of anionic polymerization, and perfluorolyethers were obtained with number-average degree of polymerization more than 15. CsF and RbF were used as catalysts and their catalytic activities were investigated. Experimental results show that perfluorolyethers with number-average molar masses up to 3 000 g/mol could be obtained using the two kinds of catalysts, respectively. As compared to CsF, the number-average degree of polymerization is higher and the relative molecular mass distribution interval is narrower when RbF is used as catalyst. The effect of factors such as impurities＇ content, reaction temperature and reaction time on the number-average degree of polymerization was also investigated. It is found that low impurities＇ content and low temperature are beneficial to the generation of high number-average degree of perfluorolyethers. The optimization reaction time is 24 h, and fiarther increase of reaction time does not significantly affect the average relative molecular mass. The product was characterized by IR, 19F NMR and GC-MS, and the catalytic mechanism was analyzed finally.

Trimethyl-1,4-Benzoquinone Synthesis via 2,3,6-Trimethylphenol Catalytic Oxidation by Oxygen in the Presence of Non-Keggin-Type Mo-V-Phosphoric Heteropoly Acid Solutions

In the present study, the modified （non-Keggin-type） aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh （HPA-x＇） were applied as homogeneous catalysts for the two-stage oxidation of TMP （2,3,6-trimethylphenol） by oxygen into TMQ （2,3,5-trimethyl-l,4-benzoquinone）, the latter being the key intermediate in the synthesis of vitamin E. The TMQ yield was analyzed regarding solvent type, reaction temperature, molar HPA-x ＇：TMP ratio, and the concentration of vanadium （V） in the HPA-x＇ solution. The TMQ yield was found to depend strongly on the catalyst redox potential and the rate of electron transfer. The results obtained enabled to establish the optimal reaction conditions as well as to suggest the reaction mechanism. In the target reaction, which proceeds in the two-phase system, the TMQ yield is higher than 99%. After phase separation, the catalyst is rapidly regenerated by oxygen and reused.

An efficient catalytic system for the synthesis of glycerol carbonate by oxidative carbonylation of glycerol

Glycerol carbonate was synthesized by the oxidative carbonylation of glycerol catalyzed by the commercial Pd/C with the aid of NaI. High conversion of glycerol （82.2%）, selectivity to glycerol carbonate （〉99%）, and TOF （900 h-1） were obtained under the conditions of 5 MPa （Pco：Po2 = 2：1）, 140 C, 2 h. The highly active palladium species were generated in situ by dissolution from the carbon support and stabilized by re-deposition onto the support surface after the reaction was finished. Palladium dissolution and re-deposition were crucial and inherent parts of the catalytic cycle, which involved heterogeneous reactions. This Pd/C catalyst could be recycled and efficiently reused for four times with a gradual decrease in activity. Moreover, the in- fluences of various parameters, e.g., types of catalysts, solvents, additives, reaction temperature, pressure, and time on the conversion of glycerol were investigated. A reaction mechanism was proposed for oxidative carbonylation of glycerol to glyc- erol carbonate.