Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Studies on crosslinking of EPDM-PE blends by thermoanalytical techniques

The effect of blend ratio and peroxide concentration on crosslinking characteristics of EPDM-PE blends were studied by Differential Scanning Calorimetry, Brabender plasticorder and Rheometer. Crosslinking of EPDM-PE blends follows first order reaction kinetics. The curing exotherm increases but activation energy decreases with increase in EPDM content in the blends. The same however increases with the increase in concentration of DCP upto a certain level, while the activation energy is almost independent of peroxide concentration. The cure rate increases whereas optimum cure time and energy consumption for curing decrease with increase in the EPDM-PE ratio. A method for determination of crosslinking efficiency in the case of blend systems was developed from high temperature modulus to predict the properties and the curing behaviour of the blends.

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Zusammenfassung Mittels DSC, Brabender Plasticorder und Rheometer wurde der Einfluß von Mischungsverhältnis und Peroxidkonzentration auf den Vernetzungsverlauf von EPDM-PE-Gemischen untersucht. Die Vernetzung von EPDM-PE-Gemischen verläuft nach einer Reaktion erster Ordnung. Je höher der Anteil von EPDM im Gemisch, um so exothermer ist die Vernetzung und um so kleiner ist die dazugehörige Aktivierungsenergie. Mit dem Anwachsen der DCP-Konzentration bis zu einem gewissen Niveau wächst der exotherme Charakter, während die Aktivierungsenergie fast unabhängig von der Peroxidkonzentration ist. Mit dem Anstieg des EPDM/PE-Verhältnisses wächst die vernetzungsgeschwindigkeit, während die optimale Vernetzungszeit und der Energieverbrauch für die Vernetzung sinken. Es wurde ein Verfahren zur Bestimmung der Vernetzungseffizienz bei Mischsystemen entwickelt, um Eigenschaften und Vernetzungsverhalten von Gemischen voraussagen zu können.

     

Silver (I)-promoted asymmetric halohydrin reaction of chiral N-enoyl-2-oxazolidinones: scope and limitations

The halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br₂/I₂) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where as electron-rich cinnamoyl substrates preferred to undergo iodohydrin reaction in aqueous acetone with moderate diastereoselectivity and enhanced diastereoselectivity was observed in aqueous THF.     

Solvent dependent analysis of isotropic Raman band shape of C=O stretching vibration

The isotropic Raman band shape corresponding to C=O stretching vibration of some molecules has been studied in neat liquids and as a function of solvent concentration using both polar and non-polar solvents. The Raman band shape was analyzed on the basis of correlation with the Lorentzian line shape by employinga simple method of linear curve fitting. In neat liquids and in low solvent concentration region, the band shape was found to be non-Lorentzian. With the gradual increase in solvent concentration the band shape approaches a Lorentzian function. The plot of the correlation coefficient for a Lorentzian shape shows a discontinuity in the intermediate range of solvent concentration. The influence of the structural characteristics of the solute and the solvent systems on the reference mode and various multipolar interactions together with the time varying spatial distribution of solvent molecules with respect to the reference molecule are expected to govern the microenvironmental fluctuations. This may be responsible for the discontinuity in the intermediate solvent concentration region.     

Degradation of rocket insulator at high temperature

The degradation of a rocket insulator compound based on ethylene propylene diene rubber (EPDM) containing asbestor, cork and iron oxide (Fe₂O₃) as fillers has been studied at high temperature (up to 600°) by using differential thermal analysis (DTA) and thermogravimetry (TG). The changes in physical properties on high-temperature aging are also reported. EPDM gum vulcanizates involving different types of diene, namely ethylidene norbornene (ENB), dicyclopentadiene (DCPD) and 1,4-hexadiene (HD), were used. In each case, the kinetic parameters for degradation have been evaluated. From these data, the lifetime of the rocket insulator compound has been found.

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Zusammenfassung Die Zersetzung einer Raketenisolator-Verbindung auf Äthylen-Propylen-Dien-Gummibasis (EPDM) mit Asbest, Kork und Eisenoxid (Fe₂O₃) als Füllstoffe wurden bei hohen Temperaturen (bis 600°) mittels Differentialthermalanalyse (DTA) und Thermogravimetrie (TG) untersucht. Die bei Hochtemperaturen eintretenden Veränderungen der physikalischen Eigenschaften sind ebenfalls angegeben. Verschiedene Typen von Dienen, nämlich Äthyliden-norbornen (ENB), Dicyclopentadien (DCPD) und 1,4-Hexadien (HD) enthaltenden EPDM-Gummivulkanisate waren Gegenstand der Untersuchung. In allen Fällen wurden die kinetischen Parameter der Zersetzung ermittelt. Aus diesen Daten wurde die Lebensdauer der Raketenisolator-Verbindung bestimmt.

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The authors are grateful to the Indian Space Research Organization for funding, and acknowledge the help and suggestions from Mr. T. S. Ram and Mr. Baby John, R.P.P., V.S.S.C., Trivandrum. The authors are also grateful to Prof. S. K. De, Rubber Technology Centre, and Prof. R. Ghosh, Chemistry Department, I.I.T., Kharagpur.

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The authors thank Mr. Asutosh Ghosh, Indian Association for the Cultivation of Science, for experimental assistance.     

Synthesis and photocatalytic properties of sunlight-responsive BiOBr–CoWO4 heterostructured nanocomposites

Efficient sunlight-responsive BiOBr–CoWO₄ heterostructured nanocomposite photocatalysts were prepared via a chemical precipitation route at 100°C in 4 hours. The prepared BiOBr–CoWO₄ heterostructures were characterized for phase identification, chemical composition, surface morphology, optical properties and surface area using various techniques. The X-ray diffraction pattern of the BiOBr–CoWO₄ nanocomposite was composed of diffraction peaks equivalent to both the tetragonal phase of BiOBr and the monoclinic phase of CoWO₄ nanoparticles. X-ray photoelectron spectral study of the BiOBr–CoWO₄ nanocomposite revealed orbitals of both BiOBr and CoWO₄ compounds. Transmission electron microscopy images revealed that spherical particles of CoWO₄ (20–25 nm) were dispersed on the surface of BiOBr. UV–visible–near-infrared spectral study of the BiOBr–CoWO₄ nanocomposite showed good visible-light absorption. Among the manufactured materials, BiOBr–CoWO₄-2 nanocomposite showed better charge carrier separation efficiency, as demonstrated by photoluminescence and time-resolved fluorescence. To study the practical utility of the prepared materials, their photocatalytic capability was examined for the degradation of rhodamine B (RhB) aqueous solution under sunlight irradiation. The photodegradation results showed that BiOBr–CoWO₄-2 nanocomposite degraded 98.69% RhB solution and the degradation constant was 0.067 min⁻¹, which was 5.6 and 22.5 times larger than that of pure BiOBr and CoWO₄ nanoparticles, respectively, after 60 minutes of sunlight irradiation. The superior photoactivity was facilitated by electron–hole pair separation and transfer driven by the heterostructure interface between BiOBr particles and CoWO₄ nanoparticles. The removal of RhB was initiated by photogenerated h⁺, O₂^{• −} and ^•OH reactive species based on the scavenger effect.     

Antioxidative and anticarcinogenic activities of methylpheophorbide a,isolated from wheat grass (Triticum aestivum Linn.)

Methylphophorbide a (MPa) has been isolated from the ethanol extract of the wheat grass plant. Its antioxidative efficacy is evaluated by hydroxyl radical scavenging activities and reducing capacity which are significantly up regulated in comparison with aqueous extract of the plant. The compound shows iron-binding capacity where the Fe²⁺ binds with MPa by two types of binding patterns with dissociation constants 157.17 and 27.89. It has antioxidative and cytotoxic effects on HeLa and Hep G2 cells. The cancerous cell survivability decreases with increasing concentration of MPa. These findings have provided evidence for the traditional use of the wheat grass plant in the treatment of cancers, oxidative stress and iron overloaded disorders.     

Reductive Cleavage of tert-Butyldimethylsilyl Ether via Intramolecular Transfer of Hydride

The cleavage of α-hydroxy tert-butyldimethylsilyl ether to diol takes place efficiently with LAH. It has been proposed that the reaction proceeds via intramolecular hydride transfer from the alkoxy aluminium hydride. In order to substantiate this, reduction of TBDMS ether with LAH in a variety of substrates was studied.