DiPAMP’s Big Brother “i‐Pr‐SMS‐Phos” Exhibits Exceptional Features Enhancing Rhodium(I)‐Catalyzed Hydrogenation of Olefins

Switching Knowles DiPAMP’s {DiPAMP=1,2‐bis[(o‐anisyl)(phenyl)phosphino]‐ ethane} MeO groups with i‐PrO ones led to the i‐Pr‐SMS‐Phos {i‐Pr‐SMS‐Phos=1,2‐bis[(o‐isoprop‐ oxyphenyl)(phenyl)phosphino]ethane} ligand which displayed a boosted catalyst activity coupled with an enhanced enantioselectivity in the rhodium(I)‐catalyzed hydrogenation of a wide‐range of representative olefinic substrates (dehydro‐α‐amido acids, itaconates, acrylates, enamides, enol acetates, α,α‐diarylethylenes, etc). The rhodium(I)‐(i‐Pr‐SMS‐Phos) catalytic profile was investigated revealing its structural attributes and robustness, and in contrast to the usual trend, ³¹P NMR analysis revealed that its methyl (Z)‐α‐acetamidocinnamate (MAC) adduct consisted of a reversed diastereomeric ratio of 1.4:1 in favour of the most reactive diastereomer.     

Modeling of dynamic mechanical properties of vulcanized fluoroelastomer

The dynamic mechanical properties of a vulcanized fluoroelastomer (FKM) were studied over a range of temperatures and shear frequencies. Dynamic mechanical analysis and differential scanning calorimetry were used for the purpose of the study. A model was developed in order to describe FKM's viscoelastic behavior at various temperatures. The model was fitted to experimental data using an algorithm, which was developed for this purpose. As a result the FKM discrete relaxation spectrum at two reference temperatures was obtained, as well as the Williams‐Landel‐Ferry (WLF) equation parameters or the activation energy equivalent. Further on, the model was applied on storage modulus and loss tangent values obtained from the experiments, during which the temperature increased linearly. It was observed that the WLF equation fits well with the results during the glass transition, while the Arrhenius‐type relationship predicted too rapid decrease of the storage modulus during the glass transition. The master curves were constructed using the previously calculated WLF parameters and the activation energy equivalent. The developed model may be readily applied for the prediction of the numerous FKM compounds' frequency–temperature behavior using the dynamic mechanical properties obtained from either isothermal or low linear heating rate program measurements. POLYM. ENG. SCI., 47:2085–2094, 2007. © 2007 Society of Plastics Engineers     

Flow through packed bed reactors: 2. Two-phase concurrent downflow

A model for the prediction of pressure drop and liquid holdup for trickling flow in packed bed reactors has been developed, based on the relative permeability concept. The relative permeabilities for gas and liquid as functions of corresponding phase saturations have been studied with 1300 newly measured data pairs of pressure drop and liquid holdup obtained for a wide range of commercially relevant operating conditions (including pressures up to 50 bar) as well as types of packing (both in terms of size and shape). The relative permeabilities are found to be solely the functions of corresponding phase saturations and it is shown that the functional form of the correlations developed, which are otherwise purely empirical by nature, has its roots in the physics of flow at the microscale level. The proposed model requires no prior experimental knowledge about the packed bed and is able to predict liquid holdup and pressure drop to within 5% and 20%, respectively, regardless of the type of packing or operating range investigated.     

The influence of the polymerization on properties of an ethylacrylate/2-ethyl hexylacrylate pressure-sensitive adhesive suspension

In this paper, the batch suspension copolymerization process for production of microsphere acrylic pressure-sensitive adhesives (PSA) is presented. The effects of different process and chemical parameters on adhesion properties are discussed. The reaction was monitored in-line by using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Properties of the adhesive suspension (particle size), adhesive (gel phase, molecular weight, glass transition temperature (T_g)) and adhesion properties (tack, peel strength and shear) were determined. The results have shown that reaction kinetics strongly depends on polymerization temperature and initiator concentration. On the other hand, adhesion properties depend mainly on the T_g of the polymer and on the amount of insoluble gel fraction in the adhesive.     

Plasma‐activated methane partial oxidation reaction to oxygenate platform chemicals over Fe,Mo, Pd and zeolite catalysts

Natural gas from stranded sources is being predominantly flared, and there is a growing demand for new technologies for its utilisation, where electrification, flexibility, and modularity play an important role. Plasma‐activated methane partial oxidation reaction was studied in a designed dielectric barrier discharge ionisation reactor unit, producing value‐added platform chemicals, namely, methanol, formaldehyde, intermediate formic acid, acetic acid, and paraformaldehyde at ambient temperature and atmospheric pressure. The effects of various process parameters, such as voltage, total convertible gas flow rate, and reagent ratio relationship, were considered. In addition, coupling of the following catalytic materials with plasma was examined: alumina (Al₂O₃), chabazite, ferrierite, microporous beta zeolite, silica (SiO₂) glass beads, ZSM‐5 (MFI), Fe on H‐ZSM‐5 and Al₂O₃, Mo on H‐ZSM‐5, TiO₂ and SiO₂, and Pd on Al₂O₃. In the liquid product, 21.5% CH₃OH, 20.4% CH₂O, 0.3% HCOOH, and 2.4% CH₃COOH were measured when using pure plasma, and a maximum aggregate yield of the organic oxygenate compounds of 5.21 mol.% was achieved. The usage of shaped silicate surface increased the selectivity towards synthesised oxygen‐containing structures, while the application of alumino‐silicate mixture constituents reduced it. It was determined that elementary covalently bonded carbon was formed inside pores when pure zeolites were used. Fe‐ and Pd‐based heterogeneous catalysts favoured the complete exothermic combustion of CH₄ feedstock reactant species, and the liquid product consisted only of water in the Pd‐ case. The utilisation of Mo/H‐ZSM‐5 resulted in a 46% increased yield of formalin. A mechanism for the role of Mo was proposed, where Mo oxidises methanol to formaldehyde and the metal is reoxidised in plasma.     

Influence of Topology of Highly Porous Methacrylate Polymers on their Mechanical Properties

Porous polymer monoliths are prepared using glycidyl methacrylate and methyl methacrylate as monomers, in both cases crosslinked with ethylene glycol dimethacrylate. Up to 75% porous samples are produced using either emulsion templating or bulk polymerization with porogens. In the case of emulsion templating, a cellular topology with cavities between 3.1 and 5.5 µm is observed for both monomers, while a cauliflower‐like topology is formed in the case of bulk polymerization. The influence of topology features of monoliths on the mechanical properties is studied and for both polymers a dramatic influence, on both compressive moduli and compressive strength, is found. The mechanical parameters, namely elastic modulus and compressive strength are significantly higher for emulsion templated samples.     

Interactive Large‐Scale Procedural Forest Construction and Visualization Based on Particle Flow Simulation

Interactive visualization of large forest scenes is challenging due to the large amount of geometric detail that needs to be generated and stored, particularly in scenarios with a moving observer such as forest walkthroughs or overflights. Here, we present a new method for large‐scale procedural forest generation and visualization at interactive rates. We propose a hybrid approach by combining geometry‐based and volumetric modelling techniques with gradually transitioning level of detail (LOD). Nearer trees are constructed using an extended particle flow algorithm, in which particle trails outline the tree ramification in an inverse direction, i.e. from the leaves towards the roots. Reduced geometric representation of a tree is obtained by subsampling the trails. For distant trees, a new volumetric rendering technique in pixel‐space is introduced, which avoids geometry formation altogether and enables visualization of vast forest areas with millions of unique trees. We demonstrate that a GPU‐based implementation of the proposed method provides interactive frame rates in forest overflight scenarios, where new trees are constructed and their LOD adjusted on the fly.     

Dual representation of spatial rational Pythagorean-hodograph curves

In this paper, the dual representation of spatial parametric curves and its properties are studied. In particular, rational curves have a polynomial dual representation, which turns out to be both theoretically and computationally appropriate to tackle the main goal of the paper: spatial rational Pythagorean-hodograph curves (PH curves). The dual representation of a rational PH curve is generated here by a quaternion polynomial which defines the Euler–Rodrigues frame of a curve. Conditions which imply low degree dual form representation are considered in detail. In particular, a linear quaternion polynomial leads to cubic or reparameterized cubic polynomial PH curves. A quadratic quaternion polynomial generates a wider class of rational PH curves, and perhaps the most useful is the ten-parameter family of cubic rational PH curves, determined here in the closed form.     

Phase transfer catalyzed esterification: modeling and experimental studies in a microreactor under parallel flow conditions

A liquid–liquid phase transfer catalyzed (PTC) esterification reaction of 4-t-butylphenol in aqueous phase (1 M sodium hydroxide solution) and 4-methoxybenzoyl chloride in organic phase (dichloromethane) in a microchannel under parallel laminar flow conditions was studied in this work. Tetrabutylammonium bromide was used as the PTC. Stable liquid–liquid hydrodynamic flow and a defined specific interfacial area in a microreactor offer considerable benefits over conventional batch reactors and are crucial to study interactions between kinetics and mass transfer effects. Mentioned features were used to develop a 3D mathematical model considering convection in the flow direction, diffusion in all spatial directions, and reactions in organic and aqueous phases. Results have shown a much higher mass transfer rate of the PTC between both phases as the one predicted by the 3D mathematical model. It may be assumed that the instability of parallel flow, along with the mass transfer of catalyst between both phases, causes rippling and erratic pulsation at the interface which then leads to interfacial convection and increased mass transfer rates. With a proposed correlation for mass transfer enhancement due to interfacial convection, all the experimental data were successfully predicted by the model.