Ring-Opening Reactions of Propylene Oxide (Methyloxirane) over Au/MgO and Unsupported Au Catalysts

The ring-opening reactions of propylene oxide (methyloxirane) were studied over an Au/MgO catalyst and Au powder at various temperatures in a pulse microreactor. The supported catalyst was significantly more active, and its activity was dramatically influenced by the method of pretreatment. When it was finished with hydrogen, conversion values were always above 70%, but often it was in the 90%+ range. The major reaction pathways were deoxygenation and isomerization. The comparison in the behavior of Au/MgO and Au powder pointed to the crucial importance of the support–metal interface in oxygen traffic and as a landing place for hydrogen-rich residues being the hydrogen source for water and alcohol formation (hydrogenation).     

Spectroscopic and Catalytic Activity Studies of VO(Saloph) Complexes Encapsulated in Zeolite-Y and Al-MCM-41 Molecular Sieves

VO(Saloph) complexes, where Saloph = N,N-o-phenylenebis(salicylide naminato), have been encapsulated in microporous zeolite NaY and mesoporous Al-MCM-41 molecular sieves by the flexible ligand synthesis method. Upon encapsulation the coordination of VO(Saloph) changes from a square pyramidal to an octahedral geometry. Encapsulation and the pore size have marked effects on the trans-stilbene and styrene epoxidation activities of VO(Saloph), with tert-butylhydroperoxide as oxidant. The encapsulated complexes are more active (by three to five times) than the neat complexes. The encapsulated complexes could easily be separated from the products and the catalysts can be reused. VO(Saloph) complexes encapsulated in Al-MCM-41 are relatively more active than the zeolite-Y-encapsulated complexes. The relaxed geometry of VO(Saloph) and easy access of the active site to the substrate molecules are perhaps responsible for the higher activity of VO(Saloph) encapsulated in Al-MCM-41.     

Mono (V, Nb) or bimetallic (V–Ti, Nb–Ti) ions modified MCM-41 catalysts: synthesis, characterization and catalysis in oxidation of hydrocarbons (aromatics and alcohols)

Mesoporous MCM-41 molecular sieves modified by single (V and Nb) or bimetal (Nb–Ti and V–Ti) ions with highly ordered hexagonal arrangement of their cylindrical channels were prepared by direct synthesis with two different silica sources (sodium silicate and TEOS) and characterized (as-synthesized samples and those used after reaction) by XRD, N₂ adsorption–desorption, TEM, SEM and FTIR techniques. Niobium and titanium were stabilized in the autoclavized gel by complexation with a ligand (acetylacetone and oxalic acid, respectively). V modified MCM-41 catalysts gave a very high activity in hydroxylation reaction of benzene and toluene and a low conversion in oxidation of styrene while Nb-modified MCM-41 samples showed very high conversion in oxidation of styrene but low oxidation conversion of benzene and toluene. Further introduction of titanium in V- and Nb-modified MCM-41 materials conducted to the less well-ordered hexagonal arrangement and gave very different effect on activity in oxidation of aromatics. Introduction of Ti into V-MCM-41 solids led to an increase in activity in oxidation of styrene and benzene but a decrease in conversion in oxidation of toluene. While the addition of Ti in Nb-MCM-41 resulted in a slight increase in conversion of styrene oxidation but a significant decrease in activity of benzene and toluene oxidation. It reveals that the introduction mode of oxidant in the reactors can also influence the activity and selectivity of reaction. An increase in reaction rate of oxidation, in the first 20 h, was obtained by introduction of H₂O₂ step by step during the reaction. The present paper evidenced that the side chain oxidation is main reaction of styrene oxidation while the hydroxylation is main reaction of benzene and toluene. That is why these two reactions need different catalytic centers as revealed by this paper. The oxidation of alcohols using V-modified MCM-41 as catalysts has also been explored and these catalysts showed a very low catalytic activity which increases in the order: hexanol相似文献   

Fire‐retardant action of resorcinol bis(diphenyl phosphate) in PC–ABS blend. II. Reactions in the condensed phase

The thermal decomposition of polycarbonate (PC), PC containing resorcinol bis(diphenyl phosphate) (RDP), and PC—acrylonitrile–butadiene–styrene (PC–ABS) blend containing RDP was studied by thermogravimetry. Volatile and solid products of thermal decomposition were collected at different steps of thermal decomposition and characterized either by gas chromatography–mass spectrometry or infrared and chemical analysis. It was found that phosphorus accumulates in the condensed phase. Upon combustion of the fire‐retardant mixture PC–ABS + RDP, accumulation of phosphorus is observed in the charred layer, at the surface of the burning specimens. It is suggested that PC undergoes a Fries‐type rearrangement upon thermal decomposition, and RDP reacts with the formed phenolic groups through a trans‐esterification mechanism. Kinetic analysis of the thermal decomposition of PC containing RDP supports the proposed mechanism. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1863–1872, 1999     

Kinetic investigation of the NO decomposition over V–O–W/Ti(Sn)O2 catalyst

A kinetic study of the NO decomposition over V–O–W/Ti(Sn)O₂ catalyst carried out in a tubular fixed-bed reactor operating under atmospheric pressure at different temperatures and at various space times is presented. Assuming that NO decomposition occurs as a result of electron transfer from the metal active site to antibonding π NO orbital, several kinetic models were derived and applied to describe the kinetics of reaction. The best agreement between the experimental data and theoretical prediction was achieved with the model assuming adsorption of NO on the active sites as the rate-determining step. Finally, it was concluded that V–O–W/Ti(Sn)O₂ catalyst has promising activity for the NO removal in O₂ presence from the effluent gases of the different sources of emission.     

Second Generation CaSH (Camphor Sulfonyl Hydrazine) Organocatalysis. Asymmetric Diels–Alder Reactions and Isolation of the Catalytic Intermediate

In one step, the well known chiral auxiliary, Oppolzer’s camphor sultam, is turned into the new generation camphor sulfonyl hydrazine (CaSH II) organocatalyst. With the primary hydrazine functionality external to the tricyclic structure, CaSH II is active towards ketone substrates in asymmetric Diels–Alder reactions. The iminium intermediate of the catalytic cycle was isolated. When it was put back into the solution reaction system, the same level of yield and stereoselectivity was observed. Based on these observations, we argue that organocatlyst is actually an in situ chiral auxiliary.     

Low temperature complete combustion of dilute toluene and methyl ethyl ketone over Mn‐doped ZrO2 (cubic) catalysts

Combustion of dilute toluene and methyl ethyl ketone over Mn‐doped ZrO₂ catalysts prepared using different precipitating agents, such as tetra‐alkyl ammonium hydroxides and NH₄OH, having Mn/Zr ratios from 0.05 to 0.67, and calcined at different temperatures has been thoroughly investigated. The Mn‐doped ZrO₂ catalyst shows high toluene or methyl ethyl ketone combustion activity, particularly when its ZrO₂ is in cubic form, when its Mn/Zr ratio is close to 0.2, and when it is prepared using tetra‐methyl ammonium hydroxide as a precipitating agent and calcined at 773 K. Copyright © 2005 Society of Chemical Industry     

Compatibilization of poly(ethylene-co-vinyl alcohol) (EVOH) and EVOH–HDPE blends: Structure and properties

Hydrogenated and maleated S-B-S block copolymer (SEBS-g-MA) was applied as a compatibilizer in melt-mixed binary blends with poly(ethylene-co-vinyl alcohol) (EVOH) and in ternaries containing high-density polyethylene (HDPE) as the major component. The techniques applied were dynamic, mechanical, and tensile testing; differential thermal analysis; Fourier transform infrared spectroscopy; and optical and electron microscopy (SEM). Small and large deformation behavior under dynamic and static mode, coupled with other physical characterization data, as well as morphological evidence, demonstrated that SEBS-g-MA is an efficient compatibilizer in the binary and ternary blends. In the latter, its function is the coupling of EVOH with the HDPE matrix, thus reducing the moisture sensitivity of the former and the improvement of performance-to-cost ratio of the final product. After leaching out EVOH from the ternaries, morphology examination of the cross section of films, showed a laminar EVOH phase distribution, a feature desirable in barrier materials applications. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 589–596, 1998     

Dilute solution properties of poly(2-methoxycyanurate) of bisphenol F and bisphenol A

Poly(2-methoxycyanurate) of bisphenol F and bisphenol A (PMCBFA) was synthesized and fractionated by a fractional precipitation method. The fractions were characterized by viscometry, osmometry and gel permeation chromatography. The Mark–Houwink–Kuhn–Sakurada (MHKS) parameters were established in four solvents and at four different temperatures. The unperturbed dimensions and their coefficients in different solvents were computed using the Stockmayer–Fixman excluded volume theory. From the solution study it was found that PMCBFA is highly flexible. This may be due to the ether linkage present in the main chain.     

Unusual Effect of α-olefins as Chain Transfer Agents in Ethylene Polymerization over the Catalyst with Nonsymmetrical Bis(imino)pyridine Complex of Fe(II) and Modified Methylalumoxane (MMAO) Cocatalyst

Ethylene polymerization with bis(imino)pyridlyiron precatalysts generally produces linear polyethylene (PE) even with the presence of α-olefins because α-olefins are not incorporated into polymeric products. Interestingly, α-olefins, such as hexene-1 or butene-1, have been found to act as effective chain transfer agents in the ethylene polymerization promoted by nonsymmetrical bis(imino)pyridyliron complexes with modified methylalumoxane (MMAO), resulting in higher catalytic activities with higher amounts of polymers with lower molecular weights, and, more importantly, narrower molecular weight distributions of the resultant polyethylenes (PE). This phenomenon confirms the assistance of α-olefins in the chain-termination reaction of iron-initiated polymerization and regeneration of the active species for further polymerization. Besides higher activities of the catalytic system, the formation of linear PE with trans-vinylene terminal groups and lower molecular weights are explained. The observation will provide a new pathway for enhancing catalytic activity and improving the quality of polyethylenes obtained by regulation of molecular weights and molecular weight distribution.     

Self‐assembled and crystallized composites made from poly(ether amine) and montmorillonite in the presence of copper(II) ions

Self‐assembled and crystallized composites made from montmorillonite (MMT) by intercalation with poly(ether amine) salts and copper(II) [Cu(II)] ions simultaneously were studied. The manipulation of the silicate unit structure of the secondary (001) lattice by physically imposed osmotic pressure on the platelet interlayer was used. Divalent copper salt assisted a strong depletion effect with balancing the counterions in the clay interlayer and resulted in the extension of the dimensions of the (001) plane by increasing the spacing expansion by more than two orders of magnitude. The simultaneous adsorption of Cu(II) and intercalation of poly(oxypropylene)amine (POP) salts onto the MMT units ultimately minimized their amorphous aggregation through electrostatic attraction between the negative surface and positive edge among the silicate units. Alternatively, the attraction force through face‐to‐face stacking on the silicate surface is proposed, and the conformation of the POP/Cu(II) complex aligned with the approaching platelets to form orderly structures. X‐ray diffraction of the MMT units exhibited a high order of reflection (i.e., (006)) in Bragg's pattern; this implied a repetitive regularity between the plate–plate distances. The high regularity disappeared when the Cu(II) adsorption exceeded the critical clay cation‐exchange capacity of 1.4. The conformation of the flexible polyether backbone was altered and could no longer sustain the plate distance and the symmetric packing was destroyed when the basal spacing was decreased from 82.6 to 18.0 Å. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hydroisomerization of model FCC naphtha over sulfided Co(Ni)–Mo(W)/MCM-41 catalysts

Deep hydrodesulfurization (HDS) of gasoline generally brings about the saturation of olefins and leads to the serious octane number losses. Conversion of linear olefins to branched ones followed by hydrogenation to isoalkanes would minimize such octane number losses. In this work, MCM-41-supported Co–Mo, Ni–Mo and Ni–W catalysts were prepared by the incipient wetness impregnation method, and compared with an industrial Co–Mo/γ-Al₂O₃ catalyst. The surface acidities were measured by the techniques of microcalorimetry and infrared spectroscopy for the adsorption of ammonia, and probed by the reaction of conversion of isopropanol. The isomerization and hydrogenation of 1-hexene as well as the HDS of thiophene were studied by using model FCC naphtha. It was found that the sulfidation enhanced significantly the surface Brønsted acidity that favored the skeletal isomerization of 1-hexene under the HDS conditions. Since the isomerization and hydrogenation of 1-hexene are the two competition reactions, the catalysts with relatively lower hydrogenation activity may have higher selectivity to the isomerization reactions. The Co–Mo/MCM-41 showed the high selectivity to the skeletal isomerization reactions due to its strong surface Brønsted acidity and the relatively low hydrogenation activity. On the other hand, the Ni–Mo/MCM-41 exhibited high hydrogenation activity and therefore low selectivity to the isomerization reactions although it possessed quite strong surface Brønsted acidity. The Ni–W/MCM-41 exhibited the low activity for the HDS of thiophene and isomerization of 1-hexene due to the poor dispersion of active metals.     

Microstructural evolution of amorphous Si2BC3N nanopowders upon heating at high temperatures: High pressures reverse the nucleation order of SiC and BN(C)

Amorphous Si₂BC₃N nanopowders (NPs) were heated at 1000‐1700°C temperatures for 30 minutes in 1 atm N₂. The changes in phases, chemical bonds, and microstructures were investigated by XRD, XPS, NMR, TEM, and first‐principles calculation. Increases in heating temperatures lead to the nucleation and growth of SiC and BN(C) grains, along with partial transformation of SiC₄ units from amorphous to β/α‐SiC, and collapse of B–C–N bonds. SiC nucleates prior to BN(C) at 1 atm, while it goes in the opposite order at high pressures (≥1 GPa). High pressures also shift the initial temperatures of crystallization of amorphous Si₂BC₃N NPs from 1400°C (1 atm) to 1150°C (5 GPa).     

Synthesis,characterization, and metal adsorption properties of tannin–phenol–formaldehyde resins produced using tannin from dried fruit of Terminalia chebula (Aralu)

In this study, tannin extracted from Terminalia chebula (Aralu) was used to produce tannin–phenol–formaldehyde resins. They were produced to obtain resins with different tannin to phenol ratio in an attempt to optimize the ion exchange capacities of resins produced. The resins made were sulfonated to improve their properties further. Bivalent cations, such as Zn²⁺, Pb²⁺, Ca²⁺, Mg²⁺, and Cu²⁺, were used to estimate the adsorption properties of both unsulfonated and sulfonated resins. The glass transitions of representative resins were estimated using differential scanning calorimeter thermograms. Fourier transform infrared spectroscopic analysis was used to gauge changes on resins by sulfonation and adsorption of cations. The glass transition values of unsulfonated, sulfonated, and metal‐adsorbed sulfonated resins showed a similar increasing trend with the increase of phenol content in the resin. The glass transition temperature values reach a plateau beyond the tannin/phenol ratio of 1 : 0.5, indicating the formation of large molar masses facilitating entanglements beyond that ratio. The phenol ratio of 1 : 0.5 has shown the highest adsorption capacity for all the metal ions used. The highest adsorption capacity was shown for sulfonated tannin–phenol–formaldehyde resin with the tannin/phenol ratio of 1 : 0.5 for Pb²⁺, which is 0.610 meq/g. The adsorption equilibrium data obtained using the column technique were found fitting Freundlich isotherm. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface Properties of CaO (or BaO)–La2O3–MgO Catalysts and Their Performance in Oxidative Coupling of Methane

CaO–La₂O₃–MgO and BaO–La₂O₃–MgO catalysts with different compositions have been studied for their bulk and surface properties (viz. crystal phases, surface area, acidity/acid strength distribution, basicity/base strength distribution, etc.) and catalytic activity/selectivity in the oxidative coupling of methane (OCM) at different processing conditions (reaction temperature, 700–850°C; CH₄/O₂ ratio in feed, 3·0, 4·0 and 8·0 and GHSV, 102000 and 204000 cm³ g⁻¹ h⁻¹). The surface acidity and strong basicity of La₂O₃–MgO are found to be increased due to the addition of a third component (CaO or BaO), depending upon its concentration in the catalyst. The addition of CaO or BaO to La₂O₃–MgO OCM catalyst causes a significant improvement in its performance. Both the CaO- and BaO-containing catalysts show a high activity and selectivity at 800°C, whereas, the activity and selectivity of BaO-containing catalysts at 700°C is lower than that of CaO-containing catalysts. © 1997 SCI.     

Influence of the matrix porosity on the synthesis and adsorption behavior of dithiocarbamate styrenic resins toward zinc(II) and cadmium(II) ions

The dependence of the adsorption behavior toward Zn²⁺ and Cd²⁺ on the synthesis conditions of dithiocarbamate styrenic resins was investigated. We synthesized styrene–divinylbenzene copolymers with different kinds of porous structures by varying the divinylbenzene (DVB)‐to‐styrene ratio and the dilution degree of the monomers with n‐heptane. The porous structure of these materials was characterized. The introduction of the dithiocarbamate moiety on the copolymers followed a synthetic pathway based on the nitration reaction, reduction of the nitro group to the amino one, and finally, the addition of the amino group to CS₂. All of the synthesis steps were monitored by Fourier transform infrared spectroscopy. Only the addition reaction to CS₂ was greatly influenced by the copolymer porosity. The effect of the dilution degree on the reaction extension was more pronounced than the effect of the DVB content. The more porous materials with higher dithiocarbamate contents adsorbed a higher amount of ions in a faster way, with Zn²⁺ being preferable over Cd²⁺ ions. The difference between the Zn²⁺ and Cd²⁺ adsorption rates was enhanced with the copolymer porosity, and also enhanced was the difference between the amounts of ions adsorbed by the copolymer; this suggested that the selectivity toward these ions could be controlled by the copolymer porous structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solution Structure and Constrained Molecular Dynamics Study of Vitamin B12 Conjugates of the Anorectic Peptide PYY(3–36)

Vitamin B₁₂–peptide conjugates have considerable therapeutic potential through improved pharmacokinetic and/or pharmacodynamic properties imparted on the peptide upon covalent attachment to vitamin B₁₂ (B₁₂). There remains a lack of structural studies investigating the effects of B₁₂ conjugation on peptide secondary structure. Determining the solution structure of a B₁₂–peptide conjugate or conjugates and measuring functions of the conjugate(s) at the target peptide receptor may offer considerable insight concerning the future design of fully optimized conjugates. This methodology is especially useful in tandem with constrained molecular dynamics (MD) studies, such that predictions may be made about conjugates not yet synthesized. Focusing on two B₁₂ conjugates of the anorectic peptide PYY(3–36), one of which was previously demonstrated to have improved food intake reduction compared with PYY(3–36), we performed NMR structural analyses and used the information to conduct MD simulations. The study provides rare structural insight into vitamin B₁₂ conjugates and validates the fact that B₁₂ can be conjugated to a peptide without markedly affecting peptide secondary structure.     

Ionic Liquid Effect on the Reversal of Configuration for the Magnesium(II) and Copper(II) Bis(oxazoline)‐Catalysed Enantioselective Diels–Alder Reaction

Ionic liquids have been used to support a range of magnesium‐ and copper‐based bis(oxazoline) complexes for the enantioselective Diels–Alder reaction between N‐acryloyloxazolidinone and cyclopentadiene. Compared with reaction performed in dichloromethane or diethyl ether, an enhancement in ee is observed with a large increase in reaction rate. In addition, for non‐sterically hindered bis(oxazoline) ligands, that is, phenyl functionalised ligands, a reversal in configuration is found in the ionic liquid, 1‐ethyl‐3‐methylimidazolium bis[(trifluoromethanesulfonyl)imide], compared with molecular solvents. Supported ionic liquid phase catalysts have also been developed using surface‐modified silica which show good reactivity and enantioselectivity for the case of the magnesium‐based bis(oxazoline) complexes. Poor ees and conversion were observed for the analogous copper‐based systems. Some drop in ee was found on supporting the catalyst due a drop in the rate of reaction and, therefore, an increase in the contribution from the uncatalysed achiral reaction.