Effect of the alkyl chloride-to-aluminum molar ratio in the catalysts of dec-1-ene oligomerization on the product distribution and the chlorine content in the products

Dec-1-ene oligomerization in the presence of an aluminum—1-dodecyl chloride system was studied. A mixture of low-molecular-weight oligodecenes containing 25–40 wt.% dimers and 30–52 wt.% dec-1-ene trimers is formed at the molar ratios RCl/A1 = 0.5–1.5. The oligomerization was assumed to occur under the action of cationic active sites, which are formed during the reaction of 1-chlorodedecane with aluminum. At temperatures of 120–130°C and molar ratios RCl/A1 = 0.5–1.5 metallic aluminum completely dechlorinates 1-chlorododecane in a dec-1-ene medium. The character of the effect of highly dispersed Al and the RCl/A1 molar rato on the fractional composition and chlorine content in oligodecenes was revealed. The latter are formed by an aluminum—tert-butyl chloride system used in the industrial oligomerization of dec-1-ene. A mechanism of Al dissolution by alkyl chlorides with the simultaneous dechlorination of alkyl chloride and formation of cationic active sites in A1-RCl systems was proposed to explain the results obtained. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 661–665, March, 2008.     

基于丙烯酸酯的全息聚合物分散液晶光栅的动力学理论研究

采用一维无限长模型分析法对全息聚合物分散液晶(HPDLC)做了动力学方面的研究，给出了相关的扩散动力学方程和聚合动力学方程,并与折射率调制度Δn相结合获得了光栅衍射效率的表达式，对HPDLC光栅性能的改善提供了理论上的指导.     

Influence of Moisture on the Structure and Properties of the Interphase Layer of a Composite Based on an Epoxy Binder with a Disperse Filler

Properties of a model composite based on an ED-22 epoxy binder, cured with polyprophylene polyamine, and disperse LiF crystals as a filler were investigated by the methods of dilatometry and X-ray diffractometry. It was established that the density of cross-links of the epoxy binder in the interphase layer was lower than in a block specimen. Therefore, the thermal expansion of the composite on heating to 120°C, in terms of that of the binder, grew significantly with the degree of filling ϕ, and the water uptake also increased at the initial stage. The presence of absorbed water led to considerable changes in the structure and properties of the composite interphase: the binder became more cross-linked, its structural ordering decreased, the thermal expansion at heating diminished by a factor of 3. 7 (at ϕ = 50%), and the glass-transition temperature increased. As a result of long-term action of moisture, changes in the internal stresses had an extreme character.__________Translated from Mekhanika Kompozitnykh Materialov, Vol. 41, No. 4, pp. 535–544, July–August, 2005.     

Soluble metal–polymer catalysts in the hydrogenation of organic compounds

Literature describing the use of soluble metal–polymer catalysts in the molecular hydrogenation of alkenes, alkynes, aromatic and heterocyclic compounds has been reviewed. Special attention has been paid to coordinated metallic and organometallic catalytic systems and highly dispersed colloidal metals stabilized with polymers. The influence of metals, polymers and solvents on the structures of active sites is discussed. The prospects for the application of soluble metal–polymer catalysts in organic synthesis are also considered.     

Atomically Dispersed Main Group Magnesium on Cadmium Sul-fide as the Active Site for Promoting Photocatalytic Hydrogen Evolution Catalysis

Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light absorption of photocatalysts,however,most of the developed photocatalysts still suffer from low photocatalytic performance due to the limited active site(s)and fast recombination of photogenerated charge carriers.In this work,atomically dispersed main group magnesium(Mg)is introduced onto CdS monodispersed nanospheres,which greatly enhances the photocatalytic hydrogen evolution reaction.The photocatalytic hydrogen evolution reaction rate reaches 30.6 mmol·gcatalyst^-1·h^-1,which is about 11.8 and 2.5 times that of pure CdS and Pt(2 wt.%)-CdS.The atomically dispersed Mg on CdS acts as an electron sink to trap photogenerated electrons,and at the same time,greatly reduces the Gibbs free energy of hydrogen evolution reaction(HER)and accelerates HER.     

颗粒弥散Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ基复合透氧膜材料的制备、结构与性能研究

Dense oxygen permeable membranes are expected to have great impact on oxygen production and oxygen involved industrial processes. Ba0.5Sr0.5Co0.8Fe0.2O3-δ is of highest oxygen permeability at elevated temperatures. A novel composite ceramic preparation route for Ba0.5Sr0.5Co0.8Fe0.2O3-δ was developed by directly produced stable BaZrO3 based secondary phase particles(SPP) via addition of ZrO2 and iso molar excess BaO, aiming at improving mechanical properties. It revealed that as synthesized composites could get a well developed and fine grained microstructure, there being secondary phase particles as the grain growth inhibitor, and the mechanical properties and oxygen permeation are improved. For the composite with addition of 10% ZrO2+10% BaO, a well developed and fine grained microstructure has been obtained. Compared to the pure phase BSCF5582, the three point bending strength of the composite with addition of 5% ZrO2+5% BaO increases by 68% and its oxygen permeation rate is much higher below 850℃ with the smaller apparent activation energy. Additionally, the electrical properties of the composites are also affected by the inclusion of SPP: conductivity decreases with the SPP content increasing, while the hysteresis of conductivity declines due to the relative stable carrier concentration.     

含Gemini表面活性剂的PVA分散液晶的微结构与性能

采用N,N'-二(十二烷基)-N,N,N',N',N″-五甲基-1,4,7-三氮杂双碘化氨为Gemini表面活性剂,液晶为4-正戊基-4'-氰基联苯(5CB),通过微胶囊法制备了聚乙烯醇(PVA)分散液晶薄膜,着重研究Gemini表面活性剂对PVA分散液晶薄膜的微结构、电光特性的影响.结果表明,加入Gemini表面活性剂仅略微增加了PVA与5CB液晶的相容性,PVA分散液晶仍保持较高的相分离程度,但是Gemini表面活性剂使液晶微滴尺寸明显变小,液晶相均匀分散地于PVA基体中,液晶指向矢构型由两极型变化为径向型,PVA分散液晶薄膜的对比度和响应速度明显提高,同时保持较低的驱动电压.     

Polymer dispersed liquid crystal device with integrated luminescent solar concentrator

Polymer dispersed Liquid crystal (PDLC) windows are regarded as a good choice for curtain-free windows. However, conventional PDLC needs external electricity to operate, which causes extra energy consumption. These devices cannot be combined with traditional solar cells for energy savings. In this study, a new design of luminescent solar concentrator (LSC)-based PDLC device is presented. In particular, we successfully demonstrate that the PDLC can be integrated with LSC as its back scatter and potentially contributes towards the enhancement of power output by minimising backside light losses. Multi-luminophore LSC is employed to increase the absorption of air mass 1.5 solar irradiance. The edge emission measurements show multiple-luminophore-based PDLC-LSC gives the maximum edge emission power which is 1.7 times more than that of single luminophore-based PDLC-LSC device. Photocurrent measurements are also performed as an additional evidence for the improved performance of PDLC-LSC device. Finally, the visual properties of PDLC-LSC devices are evaluated to realise the compatibility of using such devices in the built environment.     

Highly dispersed copper/ppm palladium nanoparticles as novel magnetically recoverable catalyst for Suzuki reaction under aqueous conditions at room temperature

An efficient procedure based on arginine‐modified Fe₃O₄@carbon magnetic nanoparticles (FCA MNPs) with highly dispersed copper nanoparticles (Cu NPs) and 92.8 ppm of Pd is reported for room temperature Suzuki reaction. For enhancing the activity of this Cu‐based heterogeneous catalyst, special arginine amino acid as a ligand with high content of heteroatoms was immobilized onto the Fe₃O₄@carbon MNPs to increase the electron density. Cu(II) ions were then loaded on the surface of the FCA MNPs and reduced to achieve uniformly dispersed Cu NPs. An aqueous mixture of metal hydroxides such as KOH, Ba(OH)₂, Ca(OH)₂, Mg(OH)₂ as a green, non‐toxic and basic medium was used for the Suzuki reaction at room temperature. This catalyst could also be recovered and reused with no loss of activity over six successful runs.     

Possibilities and Limitations of Computer Simulations of Industrial Turbulent Dispersed Multiphase Flows

We give an overview on the usage of computer simulations in industrial turbulent dispersed multiphase flows. We present a few examples of industrial flows: bubble columns and bubbly pipe flows, stirred tanks, cyclones, and a fluid catalytic cracking unit. The fluid catalytic cracking unit is used to illustrate the complexity of the physical phenomena involved, and the possibilities and limitations of the different approaches used: Eulerian–Lagrangian (particle-tracking) and Eulerian–Eulerian (two-fluid). In the first approach, the continuous phase is solved using either RANS simulations (Reynolds-Averaged Navier–Stokes simulations) or DNS/LES (Direct Numerical Simulations/Large-Eddy Simulations), and the individual particles are tracked. In the second approach, the dispersed phase is averaged, leading to two sets equations, which are quite similar to the RANS equations of single-phase flows. The Eulerian–Eulerian approach is the most commonly used in industrial applications, however, it requires a significant amount of modelling. Eulerian–Lagrangian RANS can be simpler to use; in particular in situations involving complex boundary conditions, polydisperse flows and agglomeration/breakup. The key issue for the success of the simulations is to have good models for the complex physics involved. A major weakness is the lack of good models for: the turbulence modification promoted by the particles, the inter-particle interactions, and the near-wall effects. Eulerian–Lagrangian DNS/LES can play an important role as a research tool, in order to get a better physical understanding, and to improve the models used in the RANS simulations (either Eulerian–Eulerian or Eulerian–Lagrangian).