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     

Clarification of a wheat straw‐derived medium with ion‐exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion‐exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum‐concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion‐exchange resins (A‐860S and A‐500PS) promoted considerable reductions in the content of soluble by‐products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark‐colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion‐exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose‐derived fermentation media. Copyright © 2008 Society of Chemical Industry     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

Influence of ethyl methacrylate content on the volume‐phase transition of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] microgels

A novel series of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] (p(NIPAM‐co‐EMA)) microgels was prepared by the surfactant‐free radical polymerization of N‐isopropylacrylamide (NIPAM) with ethyl methacrylate (EMA). The shape, size dispersity and volume‐phase transition behavior of the microgels were investigated by transmission electron microscopy (TEM), ultraviolet–visible (UV–Vis) spectroscopy, dynamic light scattering (DLS) and differential scanning calorimetry (DSC). The transmission electron micrographs and DLS results showed that microgels with narrow distributions were prepared. It was shown from UV–Vis, DLS and DSC measurements that the volume‐phase transition temperature (VPTT) of the p(NIPAM‐co‐EMA) microgels decreased with increasing incorporation of EMA, but the temperature‐sensitivity was impaired when more EMA was incorporated, causing the volume‐phase transition of the microgels to become more continuous. It is noteworthy that incorporation of moderate amounts of EMA could not only lower the VPTT but also enhance the temperature‐sensitivity of the microgels. The reason for this phenomenon could be attributed to changes in the complicated interactions between the various molecules. Copyright © 2004 Society of Chemical Industry     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Influence of accelerated ageing on methacrylate‐based denture resins heterogeneity as viewed by ESR‐spin‐probe method

The electron‐spin‐resonance (ESR) spin‐probe method, was used to study the heterogeneity of denture resins based on poly(methyl methacrylate). Results for three resins processed by microwave energy, conventional curing and cold curing (depending on the curing procedure and exposed to ageing in various environmental conditions) were compared. All three cured resins were stored over the same time (1200 h) in distilled water at ambient temperature and in artificial saliva at 348 K. The temperature‐dependent ESR spectra of a spin probe dispersed in the denture resins are analyzed in terms of line‐shapes and line‐widths. The appearance of two spectral components was taken as an indication of resin heterogeneity. The results reveal that the cold‐cured resin has a lower local density in comparison with microwave and conventionally cured resin. The amount of residual monomer also contributes to the local motion of polymer segments. The change of denture resins exposed to ageing is influenced both by the structure of the original resin and the ageing conditions. Restricted motion of a spin probe incorporated into the acrylic resins exposed to accelerated ageing suggests additional crosslinking of polymer chains. The differences are observed for all the investigated resins, but the highest change is observed with the cold‐cured resin. The ESR results are accompanied by T_g and T_m measurements. Copyright © 2005 Society of Chemical Industry     

High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 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