Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly (butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

The mobility of oxygen ions in CaF2

The a.c. conductivity of CaF2 samples containing a fine dispersion of CaO particles has been measured in the temperature range 630 to 1100 K. The conductivity of the dispersed solid electrolyte is two orders of magnitude higher than that for pure polycrystalline CaF2 in the middle of the temperature range. Transport measurements on pure single crystals of CaF2 and polycrystalline samples, with and without CaO dispersion, using Fe+FeO and pure Fe as electrodes, clearly indicate that fluorine ions are the only migrating ionic species with a transport number of almost unity, contrary to the suggestion of Chou and Rapp [1, 2]. The enhanced conductivity of the dispersed solid electrolyte probably arises from two effects. A small solubility of oxygen in CaF2 results in an increase in the fluorine vacancy concentration and conductivity. Adsorption of fluorine ions on the surface of the dispersed particles of CaO results in a space charge region around each particle with enhanced conductivity. Measurements on a galvanic cell incorporating CaF2 as the solid electrolyte and oxide electrodes show that the e.m.f. is a function of the activity of CaO at the electrode/electrolyte interface. The response to an oxygen potential gradient is, therefore, through an exchange reaction, which establishes an equivalent fluorine potential at the electrode/electrolyte interface.

A biomimetic total synthesis of allomicrophyllone: protective Diels-Alder reaction as a stratagem

A biomimetic total synthesis of bioactive tetracyclic natural product allomicrophyllone has been achieved in which a protective Diels-Alder reaction employing a disposable sacrificial 1,3-diene directs the regioselectivity of the subsequent Dials-Alder reaction. (C) 2010 Elsevier Ltd. All rights reserved.

Design and fabrication of an automated thermal desorption gas-solid reaction system: Oxidation of ammonia and methanol over YBa2Cu3O7−δ(123) oxide systems

A fully automated, versatile Temperature Programmed Desorption (TDP), Temperature Programmed Reaction (TPR) and Evolved Gas Analysis (EGA) system has been designed and fabricated. The system consists of a micro-reactor which can be evacuated to 10−6 torr and can be heated from 30 to 750°C at a rate of 5 to 30°C per minute. The gas evolved from the reactor is analysed by a quadrupole mass spectrometer (1–300 amu). Data on each of the mass scans and the temperature at a given time are acquired by a PC/AT system to generate thermograms. The functioning of the system is exemplified by the temperature programmed desorption (TPD) of oxygen from YBa2Cu3−xCoxO7 ± δ, catalytic ammonia oxidation to NO over YBa2Cu3O7−δ and anaerobic oxidation of methanol to CO2, CO and H2O over YBa2Cu3O7−δ (Y123) and PrBa2Cu3O7−δ (Pr123) systems.

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

One pot synthesis of polycyclic oxygen aromatics. Part IV reaction of THP ether of 2-bromomethyl phenols

Reaction of 2-bromomethyl-1-(2′-tetrahydropyranyloxy) benzene 3a with tetrachlorocatechol(TCC) in acetone in presence of anhydrous K2CO3 resulted in the formation of diastereomeric products to which cis- & trans- 6-chloro-8-hydroxy-8-(2-oxopropyl)spiro[9H-benzo[a]xanthen- 9,2′(1′H) benzofuran]-7(8H)-one (7a & 8a) structures were assigned, along with tetrachlorocatechol ethers (5a & 6a). Similar reaction of 3a with tetrabromocatechol(TBC) gave the expected monobromo compounds 7d & 8d along with the ethers 5d & 6d. When the reaction was repeated with substrates 3b–c with TCC/TBC in ketonic solvents(acetone/methyl ethyl ketone), the corresponding compounds 5b–c to 8b–c, 5e–f to 6e–f, 7e–g & 8e–h were obtained. A suitable explanation has been given for the formation of acetonyl compound 6 in this reaction.

Reaction of spironaphthalenones with hydroxylamine: Part I. A reinvestigation of the mechanism

Spironaphthalenones 1b–g on reaction with hydroxylamine hydrochloride gave the expected pyrrolotropones 2b–g. Furanotropone 6, postulated as an intermediate in the formation of pyrrolotropones, remained unchanged on reaction with hydroxylamine hydrochloride in ethanol. Reaction of unsymmetrical spironaphthalenones 1h–o with NH2OH.HCl gave the rearranged pyrrolotropones 2h–o.

Reaction of spironaphthalenones with hydroxylamine: Part II. Structure of product in the reaction of 1′-substituted spironaphthalenone.

Reaction of 1′-aryl substituted spironaphthalenones 1a–d with hydroxylamine hydrochloride in ethanol gave substituted cinnamic ester derivatives 4a–d. Similarly, reaction of spironaphthalenone 1a with different alcohols gave the corresponding esters 4i–m. Reaction of unsymmetrical spironaphthalenones 1e–h with hydroxylamine hydrochloride in presence of ethanol gave the respective esters 4e–h. All the esters were characterised by their spectral data.

Reaction of spironaphthalenones with hydroxylamine: Part III. A novel mechanism for the formation of products and trapping of an intermediate.

A mechanism involving the intermediacy of nitrene 5, formed from the oxime of spironaphthalenone 1 by acid catalysed dehydration, has been proposed to explain the formation of pyrrolotropones/pyrrolo esters from spironaphthalenones. The initially formed nitrene rearranges to the isopyrrole 6, which either undergoes sigmatropic migration to the pyrrolotropone 2 or adds alcohol to form the pyrrolo ester depending on substitution at 1′ position. The isopyrrole intermediate 6 has been trapped as a Diels-Alder adduct 8.

An examination of the BEBO model with the results of ab initio calculations of a reaction series

The BEBO (bond energy-bond order) model of Johnston and Parr is examined with the results of ab initio MO calculations on a series of metathetic reactions which involve hydrogen transfer. Energies are calculated at the 6-31G**/PMP2 = full//6-31G** level while the bond orders are estimated using the 6-31G** basis set with the geometry optimisation at the single configuration unrestricted Hartree-Fock frame. Our analysis reveals that the bond-order exponent in the BEBO theory is greater than unity for the reaction series and the entropy term becomes implicitly present in the BEBO model.

A novel double friedel-crafts reaction: A new entry into bicyclo[3.2.2]nonane system

A novel synthesis of dibenzobicyclo[3.2.2]nonane systems is described through a double Friedel-Crafts reaction.

Liquid-Liquid Interphase (Biphasic) as the Reaction Medium in the Assembly of a Hierarchy of Structures of 4,4 `-Azodibenzoic Acid with Zinc and Cadmium

The compounds Zn(C12H8N2)](2)C12N2H8(COO)(2)](2)center dot(C6H12O)center dot(H2O), I, Zn(C12H8N2)]C12N2H8(COO)(2)], II, Cd(C12H8N2)(H2O)]C12N2H8(COO)(2)]center dot(H2O), III, Zn(C10N2H8)]C12N2H8(COO)(2)]center dot 0.5(C10N2H8), IV, Cd(C12N2H8(COO)(2)center dot H2O], V, and Zn-3(mu(2)-O)(mu(3)-O)(3)]C12N2H8(COO)(2)], VI, have been synthesized by using a biphasic approach (I, III, V, VI) or regular hydrothermal method (II, IV). The compounds exhibit one (I and II), two (In), and three dimensionally (IV, V, VI) extended structures. The flexible azodibenzoate ligand gives rise to a 3-fold interpenetration (IV) when the synthesis was carried out using normal hydrothermal methods. The biphasic approach forms structures without any interpenetrations, especially in the three-dimensional structures of V and VI. Formation of Cd2O2 dimers in V and extended M-O(H)-M two-dimensional layers in VI suggests the subtle structural control achieved by the biphasic method. Transformation studies indicate that it is possible to transform I to II. Lewis acid catalytic studies have been performed to evaluate the role of the coordination environment in such reactions. All the compounds have been characterized by a variety of techniques that includes powder X-ray diffraction, infrared, thermogravitric analysis, UV-vis, photoluminescence studies.