Stereospecific adduct ion formation has been observed in the chemical ionization mass spectra (positive and negative) of certain E- and Z-1,2,3-triaryl-2-propen-1-ones. The Z isomers are found to give higher relative abundances of adduct ions than the E isomers. This has been interpreted in terms of the differences in the proton affinities of the isomers originating from their different degrees of enone resonance. Halide ion (CI? and Br?) attachment spectra of these compounds also show stereochemical differences in the relative abundances of [M]?˙ and [M+halide]? ions, though the effect is not as pronounced as in the case of the positive ion spectra. 相似文献
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.
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.
The reduction of triphenyltin piperidyl dithiocarbamate in acetone has been investigated using d.c. polarography and cyclic
voltammetry. Polarographic reduction yielded four well-defined waves, two of which were diffusion-controlled and two of which
appear to represent adsorption processes. The cyclic voltammetric study yielded results in close agreement with the polarographic
data. Results appear to indicate the release of the dithiocarbamate moiety, followed by reduction to form the triphenyltin
radical, which undergoes dimerization, as well as reduction to the triphenyltin anion. For comparison, the polarographic reduction
of triphenyltinchloride was investigated. A mechanism similar to that proposed by earlier authors for the polarographic behaviour
of tributyltin oxide was found.
For convenience, the more commonly used terminology of piperidyl dithiocarbamate is used throughout the paper, in place of
(piperidine-1-carbodithioato) triphenyltin (IV). 相似文献
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. 相似文献
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.
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.
600° (), , . , . , , 1,4- . . .
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.The authors thank Mr. Asutosh Ghosh, Indian Association for the Cultivation of Science, for experimental assistance. 相似文献
The present work examines the influence of magnetohydrodynamic field on natural convection phenomena inside a porous square enclosure with a pair of embedded hot circular cylinders. Numerical investigations are performed to understand the effects of interspacing distance between the embedded cylinders, Hartmann number, Rayleigh number and Darcy number on the thermal transport process and the total irreversibility generation. It is observed that the isotherm distribution is strongly affected by the presence of magnetic field although the distribution of streamlines remains independent of the strength of magnetic field. This underlines the fact that magnetic field strongly influences the heat transfer process and entropy generation characteristics. It reveals that the natural convection is suppressed in the presence of a higher magnetic field as evident from the reduction in Nusselt number. It is observed that an increase in the spacing between the cylinders increases the heat transfer rate, and moreover, the effect of the magnetic field on heat transfer is more pronounced at higher interspacing distance between the embedded cylinders. The heat transfer rate increases significantly with the increase in the permeability of the medium. The entropy generation rate is independent of the strength of applied magnetic field. Further, the contribution of the entropy generation owing to friction is found to be negligible in total irreversibility obtained at lower values of Rayleigh number irrespective of Darcy number. However, the contribution of irreversibility owing to heat transfer is found to be minimal at higher values of Rayleigh number.
Strange stars (ReSS) calculated from a realistic equation of state (EOS), that incorporate chiral symmetry restoration as well as deconfinement at high density [Phys. Lett. B 438 (1998) 123; Phys. Lett. B 447 (1999) 352, Addendum; Phys. Lett. B 467 (1999) 303, Erratum; Indian J. Phys. B 73 (1999) 377] show compact objects in the mass radius curve. We compare our calculations of incompressibility for this EOS with that of nuclear matter. One of the nuclear matter EOS has a continuous transition to ud-matter at about five times normal density. Another nuclear matter EOS incorporates density dependent coupling constants. From a look at the consequent velocity of sound, it is found that the transition to ud-matter seems necessary. 相似文献