A new efficient method for one‐pot conversions of aryl carboxylic acids into nitriles without solvent

A new efficient method for synthesising nitriles, important organic reagents, is reported in this paper. In an environmentally benign solvent‐free system, aryl carboxylic acids were converted into the corresponding nitriles via one‐pot reactions, by amidation with ethyl carbamate followed by dehydration with thionyl chloride, in excellent yields. The results showed that the method has the advantages of lower cost, higher yield, less pollution and greater ease of work‐up. Copyright © 2008 Society of Chemical Industry     

Cooling and Solidification of Melted Drops in an Immiscible Cooling Medium

The cooling and solidification of melted drops during their movement in an immiscible cooling medium is widely employed for granulation in the chemical industry, and a study of these processes to provides a basis for the design of the granulation tower height and the temperature of the cooling medium is reported. A physical model of the cooling and solidification of the drop is established and the numerical calculation is performed. The influences of the key factors in the solidification, i.e., Bi number, drop diameter, temperature of the cooling medium, etc. are presented. The cooling and solidification during wax granulation in a water‐cooling tower and during urea granulation in an air‐cooling tower (spraying tower) are described in detail. Characteristics of the solidification and temperature distribution within the particle at different times are shown. The model and calculations can be used for structure design of the granulation tower and optimization of the operation parameters.     

Gasification of Biogenic Solid Fuels

As a result of shrinking fossil fuels, biomass as a regenerative energy source gains importance. To realize biomass projects it is essential to investigate in convenient thermal procedures. On this evidence an analysis and evaluation of diverse gasification technologies with different boundary conditions and diverse biomasses are indispensable. Form and kind of the biomass as well as the type of the gasification plant cause different compositions of the product gas. The gasifiers show advantages and disadvantages concerning the biomass and the produced gas quality, depending on reactor type, kind of heat supply, gasification medium, and the pressure ratio in the reactor. As the ideal gasifier for different biomass is presently not available, it will be shown, which biomass is suitable for fixed bed or fluidized bed gasifiers.     

Structure and properties of CE/CTBN/EP blends: II. Effect of EP on the mechanical properties and thermostability of the CE/CTBN system

Carboxyl‐terminated butadiene‐acrylonitrile rubber (CTBN) has often been used to improve the toughness of cyanate ester (CE) resin while sacrificing modulus and thermostability. In this paper, the addition of the appropriate amount of epoxy resin (EP) to the CE/CTBN system is shown to not only increase the modulus and thermostability of the blend, but also improve the toughness. The values of impact strength showed a maximum for the CE/CTBN/EP 100/5/5 blend. The temperature of 10 % weight loss (T₁₀) improves from 376 °C for CE/CTBN 100/5 to 407 °C for the CE/CTBN/EP 100/5/2.5 blend. It is proposed that addition of the appropriate amount of EP can decrease the mobility and increase the stability of CTBN via the reaction between the terminal carboxyl group of CTBN and the hydroxyl group of EP. But a very high EP concentration will decrease the crosslinking density of CE, consequently reducing the mechanical properties and thermostability of the blends. Copyright © 2004 Society of Chemical Industry     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

Rheological and drug‐release behaviour of a scleroglucan gel matrix at different drug loadings

The aim of this study was to investigate the drug‐loading effects on release and mechanical properties of a scleroglucan gel, with the intention of considering them in delivery systems formulations. The rheological and kinetic properties of a 2 % w/w scleroglucan gel matrix loaded with 0, 0.02, 0.04, 0.06, 0.2 and 0.4 % w/w of theophylline (Th, used as a model drug) were investigated. Rheological measurements were performed in a controlled‐stress rotational‐shear rheometer under isothermal conditions. For theophylline release from the gel a flat Franz cell was used and the kinetic parameters were derived applying a semi‐empirical power law. The influence of scleroglucan molar weight on kinetic and rheological behaviour was also studied. Results suggest two possible effects of drug loading on the gel network: in the 0.04–0.06 % w/w Th range a plasticizing effect and in the 0.2–0.4 % w/w Th range a rigidization effect. In the first range mentioned, the changes in the gel structural properties tested by means of rheological measurements are coincident with changes in drug‐release kinetics. Copyright © 2005 Society of Chemical Industry