Kinetics for benzoylation of sodium 4-acetylphenoxide via third-liquid phase in the phase-transfer catalysis

In this research, the kinetics for synthesizing 4-acetylphenyl benzoate (R^*COOR) from benzoylation of sodium 4-acetylphenoxide via third-liquid phase-transfer catalysis was investigated. The reaction rate was observed to be strongly dependent on agitation speeds in the third-phase catalytic reaction. By forming the third-liquid phase, the observed reaction can be greatly enhanced to give a product yield of 100% in a duration of 3 min at 20 °C and 200 rpm. If a third-liquid phase was not formed in the liquid–liquid system, the reaction rate is very slow and the product yield is only 2% in 3 min at 20 °C. The reaction conducted in third-liquid phase-transfer catalytic system is faster than that in LLPTC system by 25–28 times. The amount of catalytic intermediate (QOR) in the third-liquid phase was about 50% of the catalyst initially added and kept about 30% of it remained after 1 min, and only small amounts of a catalytic intermediate residing in the organic phase were observed during the reaction using methyl t-butyl ether as the solvent. The concentration of catalytic intermediate slightly decreased with increasing reaction time, while the molar ratio of QOR to benzyl tri-n-butylammonium cation in the third-liquid phase remained almost constant after 1 min and increased with increasing agitation speeds. The experimental results were well described by the pseudo-first-order kinetics. The present work shows an effective method to synthesize 4-acetylphenyl benzoate.     

甲酸甲酯合成与转化的催化技术

本文评述了甲酸甲酯(MF)合成与转化的催化技术,展示了从MF出发发展C_1化学的可能途径,在MF的合成方面详细地分析了从甲醇出发的羰化法、脱氢法和氧化法催化技术,简介了我们的有关研究工作。     

Synthesis of Biodiesel from Soybean Oil using Heterogeneous KF/ZnO Catalyst

Biodiesel was produced by transesterification of soybean oil with methanol using ZnO loaded with KF as a solid base catalyst. It was found that the catalyst with 15 wt.% KF loading and calcined at 873 K showed the optimum activity. XRD, IR and Hammett indicator method were employed for the catalyst characterization. The results showed the activity of the catalysts was correlated with their basicity. The influence of various reaction variables on the conversion was also discussed.     

Facile preparation of amphiphilic oxyethylene-oxypropylene block copolymers by selective triazine coupling

A novel synthetic route for preparing high molecular weight poly(oxyalkylene) block copolymers has been developed by using 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride, cc) as the coupling core. The coupling reaction involves the selective substitutions of oligo(oxyalkylene)-amines onto three chlorides of the triazine ring in a stepwise manner at 0, 25 and 130 °C. By judiciously selecting the starting amines and reaction conditions, one can tailor the copolymer structures with different block configurations (tri-block, multi-block, random and alternating block). The prepared copolymers can have a high molecular weight, up to 25,600 g/mol (GPC polydispersity=1.48), and also high thermal stability due to the presence of triazine functionalities. The copolymers with hydrophilic and hydrophobic oligo(oxyalkylene) blocks are of versatile properties in solubility (water soluble or water insoluble) and morphology (crystalline or amorphous). With a specific structure of alternating oligo(oxyethylene)/oligo(oxypropylene) blocks (2000 g/mol each block), the copolymer exhibits the property of self-association. It reduces the interfacial tension of toluene/water as low as 0.5 dyne/cm at the critical micelle concentration of 0.01 wt%.     

Preparation of Titanium Nitride/Alumina Laminate Composites

A preparation route for TiN/Al₂O₃ laminate composites has been described. A water-based process using Al₂O₃ and TiN slurries with solids contents of 40 and 35 vol%, respectively, was used to make TiN and Al₂O₃ tapes. The removal of the binder was monitored by weight-loss measurements in a thermogravimetry unit. Bodies composed of Al₂O₃ and TiN tapes were densified at temperatures of 1400° and 1500°C using the Spark Plasma Sintering^® (SPS) technique. Densities of >98% of the theoretical densities were approached. Crack-free and almost fully densified TiN/Al₂O₃ compacts were prepared by heating the burned-out green bodies to the final sintering temperature (1500°C) at a rate of 100°C/min, and with a holding time of 5–10 min, under a pressure of 75 MPa. The microstructures of the obtained compacts were studied using scanning electron microscopy. Grain sizes in the sintered Al₂O₃ and TiN compacts were similar to those of the precursor powders. Hardness and indentation fracture toughness were measured at room temperature, and the monolithic compacts as well as the laminate composites exhibited anisotropic mechanical behavior; i.e., the cracks propagated much more easily in a direction parallel to the laminas than perpendicular to them.     

高聚合度聚氯乙烯的加工性能

本文对高聚合度聚氯乙烯(H-PVC)的发展及其优异的物理机械性能作了简要介绍;着重分析了H-PVC的加工性能和表征方法,并讨论了分子特性和颗料特性及加工组成、加工条件对加工性能的影响,提出了改进H-PVC加工性能的方法。     

Stability analysis and controller synthesis for discrete uncertain singular fuzzy systems with distinct difference matrices in the rules

This paper mainly studies an extended discrete singular fuzzy model incorporating the multiple difference matrices in the rules and discusses its stability and design issues. By embracing additional algebraic constraint, traditional discrete Takagi-Sugeno (T-S) fuzzy model can be extended to a generalised discrete singular Takagi-Sugeno (GDST-S) model with individual difference matrices E_i in the locally singular models, where it can describe a larger class of physical or non-linear systems. Based on the linear matrix inequality (LMI) approach, we focus on deriving some explicit stability and design criteria expressed by the LMIs for the regarded system. Thus, the stability verification and controller synthesis can be performed by the current LMI tools. Finally, some illustrative examples are given to illustrate the effectiveness and validity of the proposed approach.     

A generalized method for correcting instrument spreading in gel permeation chromatography

A general method of chromatogram correction for skewed instrument spreading in gel permeation chromatography is presented. The correction method is so general that there is no restriction on the shape of the spreading function. It admits nonsymmetric, non-Gaussian as well as nonconvolution type. Aspects of solution techniques are discussed and an illustrative example is given to elucidate the method.     

射流流化床内流体力学行为的模拟研究

以流化床应用为代表的气固流动系统是许多化工过程中的重要组成部分 ,CFD( computational fluid dynamics)方法能够为其优化设计和放大提供所需要的信息 .本文采用双欧拉模型 ,与 Gidaspow等的实验结果进行了对比 ,模拟了二维射流流化床内气泡的形成规律 ,得到了带锥型分布器的流化床内瞬时空隙率和气固相速度分布等流体力学参数 .对锥型分布器流化床的实验结果表明 ,模拟得到的气泡的形状与实验现象相接近 .     

Studies of microhardness and mar resistance using a scanning probe microscope

Scanning probe microscopy (SPM) is in a period of rapid development. It shows great promise for characterizing coating surfaces. This paper describes modification of an SPM so that it can be used to mar the surfaces of coatings under controlled conditions and to characterize the mars. Mar resistance of coatings is analyzed in terms of a ‘three response, two mechanism model.' The three responses (fracture, elastic, and plastic) can be measured quantitatively using the SPM. Of the three responses, only two (fracture and plastic deformation) are marring mechanisms – elastic deformations recover instantaneously. In some cases mars resulting from plastic deformation may recover slowly with time or with immersion in water; this phenomenon is attributed to viscoelastic creep. Microhardness is also measured with the modified SPM. Some thermoset coatings appear to be substantially harder near their surfaces than in the mass of material, and such materials may respond quite differently to stress applied at different levels near the surface. This finding has important implications for all coating properties that are strongly influenced by the surface. A quantity called ‘micro mar resistance' is defined. It may be useful for comparing different coatings under specified conditions of marring. However, there can be no single quantity that expresses ‘mar resistance' of a coating under all conditions.