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Different Catalysts (different + catalyst)
Selected AbstractsA Density Functional Study of Ethylene Insertion into the M-methyl (M = Ti, Zr) Bond for Different Catalysts, with a QM/MM Model for the Counterion, B(C6F5)3CH3,ISRAEL JOURNAL OF CHEMISTRY, Issue 4 2002Kumar Vanka Single site homogeneous catalysts have been studied extensively in recent years as alternatives to traditional heterogeneous catalysts. The current theoretical study uses density functional theory to study the insertion process of the ethylene monomer into the titanium-carbon chain for contact ion-pair systems of the type [L1L2TiCH3 -,-CH3 -B(C6F5)3], where L1, L2, are Cp, NPH3, and other ligands. Different modes of approach cis and trans to the ,-CH3 bridge were considered. The counterion, B(C6F5)3CH3,, was modeled by QM/MM methods. The value of ,Htot,the total barrier to insertion,was found to be positive (in the range of 4,15 kcal/mol). The ability of the ancillary ligands, L1 and L2, to stabilize the ion-pair was found to be an important factor in determining the value of ,Htot. On replacing the titanium metal center with zirconium, the ,Htot values were found to be lowered (in the range of 2,9 kcal/mol), indicating that they would be better catalysts than their titanium analogues. The size of the ligands L1 and L2 was increased by replacing hydrogens in the ligands with tertiary butyl groups. The value of ,Htot was found to increase (in the range of 10,28 kcal/mol) in contrast to the simple systems, for both the cis and trans cases of approach, with the cis mode of approach giving lower values of ,Htot. Solvent effects were incorporated with cyclohexane (, = 2.023) as the solvent, and were found to have a minor influence, ±(0.5,1.5) kcal/mol) on the insertion barrier for all the cases studied. [source] Synthesis of single-walled carbon nanotubes with the laser vaporization method: Ex situ and in situ measurementsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 13 2006M. Cau Abstract In situ measurements were executed in the continuous wave CO2 -laser vaporization synthesis of single-walled carbon nanotubes (SWCNTs). The results were compared with the findings of the ex situ analysis of the product. Different catalysts (Co, Ni, Co/Ni, Ni/Y and Co/Y) were used and the temperature of the target surface (Ts) changed to compare the efficiency of the synthesis process. Our main results are related to the SWCNTs diameter which is depending on Ts and on the catalysts nature. The targets containing Y with Co or Ni atoms produce more and larger SWCNTs than Co/Ni targets. The SWCNTs' diameter is seen to increase with Ts. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Effect of chain architecture on biaxial orientation and oxygen permeability of polypropylene filmJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008P. Dias Abstract Films of two isotactic propylene homopolymers prepared with different catalysts and a propylene/ethylene copolymer were biaxially oriented under conditions of temperature and strain rate that were similar to those encountered in a commercial film process. The draw temperature was varied in the range between the onset of melting and the peak melting temperature. It was found that the stress response during stretching depended on the residual crystallinity in the same way for all three polymers. Biaxial orientation reduced the oxygen permeability of the oriented films, however, the reduction did not correlate with the amount of orientation as measured by birefringence, with the fraction of amorphous phase as determined by density, or with free volume hole size as determined by PALS. Rather, the decrease in permeability was attributed to reduced mobility of amorphous tie molecules. A single one-to-one correlation between the oxygen permeability and the intensity of the dynamic mechanical ,-relaxation was demonstrated for all the polymers used in the study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] A quantitative morphological analysis of nanostructured ceria,silica composite catalystsJOURNAL OF MICROSCOPY, Issue 2 2008M. MOREAUD Summary This study aims at examining the morphology of different catalysts, which are based on a dispersion of ceria nanoparticles embedded in a high surface area mesoporous silica framework. In order to fully describe the mesostructured composite material, we propose here a quantitative description of the microstructure based on a quantitative analysis of micrographs that were obtained via high-resolution transmission electron microscopy. We have therefore developed an automatic image analysis process in order to automatically and efficiently extract all the components of the catalyst images. A statistical and a morphological analysis of the spatial arrangement of the components of the catalyst are also presented. The study shows clear differences between the materials analysed in terms of the spatial arrangement and the total surface area of the ceria phase emerging into the pores, parameters of prime importance for the catalytic properties. Thus, the silica,ceria nanostructured composite materials, displaying large surface area up to 300 m2 g,1 are shown to exhibit highly rugged surfaces resulting from ceria nanoparticles emerging in the pores. [source] Quantitative structure,reactivity relationship studies on the catalyzed Michael addition reactionsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 6 2009Bahram Hemmateenejad Abstract Quantitative structure,reactivity relationship (QSRR) can be considered as a variant of quantitative structure,property relationship (QSPR) studies, where the chemical reactivity of reactants or catalysts in a specified chemical reaction is related to chemical structure. In this manner, the Michael addition of some different substrates using different catalysts (SDS, silica gel, and ZrOCl2) was subjected to structure,reactivity relationship, quantitatively. Multiple linear regression (MLR) and partial least square (PLS) were used to perform the QSRR analysis. The resulted models for different catalyzed reactions showed that the catalysts probably act in different mechanisms since the models obtained for the catalysts included different parameters from substrate and enones. Overall, it was found that the reactivity in Michael addition reactions is controlled by coulombic (dipole and charge) interactions as well as the orbital energetic parameters. In the presence of different catalysts, the relative importance of these parameters is changed and hence the catalytic activity is changed. Copyright © 2008 John Wiley & Sons, Ltd. [source] Polycondensation Kinetics of Lactic AcidMACROMOLECULAR REACTION ENGINEERING, Issue 6 2007Yogesh M. Harshe Abstract The direct polycondensation of D,L -lactic acid in the absence and presence of different catalysts at various temperatures has been studied experimentally. Two types of reactions were carried out, one under closed conditions to estimate the equilibrium constant and the other under flow of nitrogen to estimate the polymerization rate constant. A mathematical model was developed based on a suitable kinetic scheme for polycondensation reaction accounting for the rate of water removal. The effects of different operating conditions (temperature and pressure) on the average molecular weight of the polymer have been explored through experiments and model simulations. [source] Curing of diglycidyl ether of bisphenol-A epoxy resin using a poly(aryl ether ketone) bearing pendant carboxyl groups as macromolecular curing agentPOLYMER INTERNATIONAL, Issue 8 2009Fuhua Liu Abstract BACKGROUND: Reactive thermoplastics have received increasing attention in the field of epoxy resin toughening. This paper presents the first report of using a novel polyaryletherketone bearing one pendant carboxyl group per repeat unit to cure the diglycidyl ether of bisphenol-A epoxy resin (DGEBA). The curing reactions of DGEBA/PEK-L mixtures of various molar ratios and with different catalysts were investigated by means of dynamic differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy methods. RESULTS: FTIR results for the DGEBA/PEK-L system before curing and after curing at 135 °C for different times demonstrated that the carboxyl groups of PEK-L were indeed involved in the curing reaction to form a crosslinked network, as evidenced by the marked decreased peak intensities of the carboxyl group at 1705 cm,1 and the epoxy group at 915 cm,1 as well as the newly emerged strong absorptions of ester bonds at 1721 cm,1 and hydroxyl groups at 3447 cm,1. Curing kinetic analysis showed that the value of the activation energy (Ea) was the highest at the beginning of curing, followed by a decrease with increasing conversion (,), which was attributed to the autocatalytic effect of hydroxyls generated in the curing reaction. CONCLUSION: The pendant carboxyl groups in PEK-L can react with epoxy groups of DGEBA during thermal curing, and covalently participate in the crosslinking network. PEK-L is thus expected to significantly improve the fracture toughness of DGEBA epoxy resin. Copyright © 2009 Society of Chemical Industry [source] Synthesis and characterization of hydrogels containing biodegradable polymersPOLYMER INTERNATIONAL, Issue 7 2008Adina Cretu Abstract BACKGROUND: Amphiphilic block and graft copolymers constitute a very interesting class of polymers with potential for biomedical applications, due to their special characteristics, which derive from the combination of properties of hydrophilic and hydrophobic moieties. In this work, the synthesis and biodegradation of poly(2-hydroxyethyl methacrylate)- graft -poly(L -lactide) are studied. RESULTS: The graft copolymers were synthesized using the macromonomer technique. In a first step, methacryloyl-terminated poly(L -lactide) macromonomers were synthesized in a wide molecular weight range using different catalysts. Subsequently, these macromonomers were copolymerized with 2-hydroxyethyl methacrylate in order to obtain a graft copolymer. These new materials resemble hydrogel scaffolds with a biodegradable component. The biodegradation was studied in hydrolytic and enzymatic environments. The influence of different parameters (molecular weight, crystallinity, ratio between hydrophilic and hydrophobic components) on the degradation rate was investigated. CONCLUSION: Based on this study it will be possible to tailor the release properties of biodegradable materials. In addition, the materials will show good biocompatibility due to the hydrophilic poly(2-hydroxyethyl methacrylate) hydrogel scaffold. This kind of material has potential for many applications, like controlled drug-delivery systems or biodegradable implants. Copyright © 2008 Society of Chemical Industry [source] Partial Oxidation of 4- tert -Butyltoluene Catalyzed by Homogeneous Cobalt and Cerium Acetate Catalysts in the Br,/H2O2/Acetic Acid System: Insights into Selectivity and MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2007Abstract The partial oxidation of 4- tert -butyltoluene to 4- tert -butylbenzaldehyde by hydrogen peroxide in glacial acetic acid, catalyzed by bromide ions in combination with cobalt(II) acetate or cerium(III) acetate, has been studied in detail. Based on the observed differences in reaction rates and product distributions for the different catalysts, a reaction mechanism involving two independent pathways is proposed. After the initial formation of a benzylic radical species, either oxidation of this intermediate by the metal catalyst or reaction with bromine generated in situ occurs, depending on which catalyst is used. The first pathway leads to the exclusive formation of 4- tert -butylbenzaldehyde, whereas reaction of the radical intermediate with bromine leads to formation of the observed side products 4- tert -butylbenzyl bromide and its hydrolysis and solvolysis products 4- tert -butylbenzyl alcohol and 4- tert -butylbenzyl acetate, respectively. The cobalt(II) catalysts Co(OAc)2 and Co(acac)2 are able to quickly oxidize the radical intermediate, thereby largely preventing the bromination reaction (i.e., side-product formation) from occurring, and yield the aldehyde product with 75,80,% selectivity. In contrast, the cerium catalyst studied here exhibits an aldehyde selectivity of around 50,% due to the competing bromination reaction. Addition of extra hydrogen peroxide leads to an increased product yield of 72,% (cerium(III) acetate) or 58,% (cobalt(II) acetate). Product inhibition and the presence of increasing amounts of water in the reaction mixture do not play a role in the observed low incremental yields. [source] Ruthenium-Catalyzed Asymmetric Epoxidation of Olefins Using H2O2, Part II: Catalytic Activities and MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2006Man Kin Tse Dr. Abstract Asymmetric epoxidation of olefins with 30,% H2O2 in the presence of [Ru(pybox)(pydic)] 1 and [Ru(pyboxazine)(pydic)] 2 has been studied in detail (pybox=pyridine-2,6-bisoxazoline, pyboxazine=pyridine-2,6-bisoxazine, pydic=2,6-pyridinedicarboxylate). 35 Ruthenium complexes with sterically and electronically different substituents have been tested in environmentally benign epoxidation reactions. Mono-, 1,1-di-, cis - and trans -1,2-di-, tri-, and tetra-substituted aromatic olefins with versatile functional groups can be epoxidized with this type of catalyst in good to excellent yields (up to 100,%) with moderate to good enantioselectivies (up to 84,% ee). Additive and solvent effects as well as the relative rate of reaction with different catalysts have been established. It is shown that the presence of weak organic acids or an electron-withdrawing group on the catalyst increases the reactivity. New insights on the reaction intermediates and reaction pathway of the ruthenium-catalyzed epoxidation are proposed on the basis of density functional theory calculation and experiments. [source] Ring-Closing Olefin Metathesis on Ruthenium Carbene Complexes: Model DFT Study of StereochemistryCHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2005Sergei F. Vyboishchikov Dr. Abstract Ring-closing metathesis (RCM) is the key step in a recently reported synthesis of salicylihalamide and related model compounds. Experimentally, the stereochemistry of the resulting cycloolefin (cis/trans) depends strongly on the substituents that are present in the diene substrate. To gain insight into the factors that govern the observed stereochemistry, density functional theory (DFT) calculations have been carried out for a simplified dichloro(2-propylidene)(imidazole-2-ylidene)ruthenium catalyst I, as well as for the real catalyst II with two mesityl substituents on the imidazole ring. Four model substrates are considered, which are closely related to the systems studied experimentally, and in each case, two pathways A and B are possible since the RCM reaction can be initiated by coordination of either of the two diene double bonds to the metal center. The first metathesis yields a carbene intermediate, which can then undergo a second metathesis by ring closure, metallacycle formation, and metallacycle cleavage to give the final cycloolefin complex. According to the DFT calculations, the stereochemistry is always determined in the second metathesis reaction, but the rate-determining step may be different for different catalysts, substrates, and pathways. The ancillary N-heterocyclic carbene ligand lies in the Ru-Cl-Cl plane in the simplified catalyst I, but is perpendicular to it in the real catalyst II, and this affects the relative energies of the relevant intermediates and transition states. Likewise, the introduction of methyl substituents in the diene substrates influences these relative energies appreciably. Good agreement with the experimentally observed stereochemistry is only found when using the real catalyst II and the largest model substrates in the DFT calculations. [source] | |||||||||||||