Search results for "carbon"
showing 10 items of 6057 documents
γ-radiation-initiated polymerization of vinylidene fluoride in dense carbon dioxide
2002
The γ-ray-initiated batch polymerization of vinylidene fluoride (VF2) has been investigated in dense carbon dioxide under relatively mild operative conditions (T ≤ 40 °C and P < 25 MPa). When the initial VF2 molar concentration was increased from 3.4 to 6.4 mol/L, monomer conversion increased from 20 to 73%; a similar trend was observed for the number-average molecular weight and the molecular complexity of synthesized poly(vinylidene fluoride) (PVDF) as determined from rheological measurements. Under all adopted experimental conditions, a synthesized PVDF polymer was collected in the form of a white powder. Despite the inherent heterogeneous character of the polymerization process, a homog…
NMR and Quantum-Chemical Study on the Structure of Ester Enolate−Aluminum Alkyl Complexes as Models of the Active Center in the Anionic Polymerizatio…
1999
6Li and 13C NMR on ethyl α-lithioisobutyrate (EiBLi) and quantum-chemical (DFT) calculations on methyl α-lithioisobutyrate (MiBLi) were used to elucidate the structure of the active center in the anionic polymerization of methacrylates in the presence of triethylaluminum (AlEt3) in toluene. This study reveals ester enolate/aluminum alkyl complexes with different degrees of association, (MiBLi·AlEt3)n (n = 1, 2, 4), and different stoichiometries, MiBLi·xAlEt3 (x = 1, 2). In the presence of methyl pivalate (MPiv), which is taken as a model compound for the monomer and polymer, complexes such as (MiBLi·MPiv·AlEt3)n (n = 1, 2) are formed. These complexes can dissociate into MiBLi·2AlEt3 and MPi…
Mechanism of Trichloroethene Hydrodehalogenation: A First-Principles Kinetic Monte Carlo Study
2014
A hydrodehalogenation (HDC) reaction of trichloroethene (TCE) has gained a lot of interest due to its possible application in water purification, but the reaction mechanism has been subject to much controversy. In this work, HDC of TCE on Pd(111) was examined by carrying out kinetic Monte Carlo simulations based on DFT-calculated thermodynamic and kinetic parameters. Obtained kMC results show that the HDC follows a so-called direct pathway, which means that, after adsorption on a catalyst, TCE quickly dechlorinates, producing CH–C and then, more slowly, hydrogenates to form hydrocarbon products. This is reflected in the surface coverage snapshots, where intermediates corresponding to the di…
Oxyfunctionalization of Aliphatic Esters by Methyl(trifluoromethyl)dioxirane
1996
The oxidation of lineal, cyclic, and bicyclic aliphatic p-chlorobenzoic and p-chorobenzenesulfonic acid esters 2 with methyl(trifluoromethyl)dioxirane (TFDO) (1) occurs at positions in the hydrocarbon chain distant from the directing group with a significant degree of selectivity to give the corresponding keto or hydroxy esters. Compounds 2 are relatively deactivated with respect to this oxidation due to the electron-withdrawing nature of the ester moiety. Methylene Cα−H and Cβ−H bonds remain unchanged in all cases, but tertiary Cβ−H bonds undergo oxidation with TFDO (1). Stereoelectronic factors are used to explain the faster reaction rate in competition experiments for the oxidation of en…
Single-pump heart-cutting two-dimensional liquid chromatography applied to the determination of fatty alcohol ethoxylates.
2014
Abstract A setup for heart-cutting bi-dimensional liquid chromatography (LC–LC), constructed with a chromatograph provided with a single pump, an auxiliary 6-port 2-position valve (V 6/2 ) and a column selector valve (V CS ), is described. The possible ways of connecting the two valves for LC–LC, namely with V 6/2 first followed by V CS and vice versa, are compared. The possibility of using the setups for preconcentration followed by the backwards transfer of the preconcentrated solutes to the detector or to a second column is also shown. The V 6/2 -first configuration for LC–LC was applied to the characterization of industrial fatty alcohol ethoxylates (FAEs) using UV–vis detection. For th…
Effect of ramp size and sample spinning speed on CPMAS 13C NMR spectra of soil organic matter
2011
Abstract Cross polarization (CP) magic angle spinning (MAS) 13C NMR spectroscopy is a solid state NMR technique widely applied to study the chemical composition of natural organic matter. In high magnetic fields (>7 T), fast sample spinning is required in order to reduce the influence of spinning sidebands underlying other chemical shift regions. As the spinning speed increases, the Hartmann–Hahn matching profiles break down into a series of narrow matching bands. In order to account for this instability variable amplitude cross polarization techniques (e.g. VACP, ramp-CP) have been developed. In the present study, we experimentally verified the stability of the Hartmann–Hahn condition unde…
O-Alkylation of a lignite humic acid by phase-transfer catalysis
2006
A mild phase-transfer catalytic reaction has been conducted to O-alkylate the acidic functions of a lignite humic acid (HA), using tetrabutylammonium hydroxide as the phase-transfer catalyst. The HA acidic functional groups were made to react, in tetrahydrofuran, by nucleophilic substitution with several alkyl halides-methyl iodide, and ethyl, propyl, and butyl, and benzyl bromide. The occurrence of the O-alkylation reaction was assessed by elemental analysis and 1H NMR, CPMAS 13C NMR, and FTIR spectroscopy. Bonding of alkyl groups increased the carbon and hydrogen content and the H/C ratios of all the humic reaction products. Increased nitrogen in the reaction products suggested incomplete…
Investigation of Multicomponent Sorption in Polymers from Fluid Mixtures at Supercritical Conditions: The Case of the Carbon Dioxide/Vinylidenefluor…
2008
The simultaneous sorption of carbon dioxide and vinylidene fluoride (VDF) in poly(vinylidenefluoride) from their supercritical (sc) mixtures was studied using an experimental method, already described in a previous publication, based on the gas-chromatographic determination of the equilibrium composition of the fluid phase in contact with the polymer. Argon was added to the system as a nonabsorbable molecular probe in the polymer to take into account the effect of the volume swelling on the measurement. Sorption behavior has been studied at 50 °C by changing the composition and the density of the supercritical phase. We have found that VDF dissolves in its polymer with concentrations much l…
ChemInform Abstract: Toward an Understanding of the Mechanisms of the Intramolecular [5 + 2] Cycloaddition Reaction of γ-Pyrones Bearing Tethered Alk…
2000
The molecular mechanism for the intramolecular [5 + 2] cycloaddition reaction of β-silyloxy-γ-pyrones bearing tethered alkenes has been characterized using ab initio methods. A comparative study for this sort of cycloaddition carried out at different computational levels points out that the B3LYP/6-31G* calculations give similar barriers to those obtained with the MP3/6-31G* level. Analysis of the energetic results shows that the reaction takes place along a stepwise process: first, the migration of the neighboring silyl group to the carbonyl group of the γ-pyrone takes place to give a weak oxidopyrylium ylide intermediate, which by a subsequent concerted intramolecular [5 + 2] cycloadditi…
Watching the photo-oxidation of a single aromatic hydrocarbon molecule
2001
International audience; The photooxidation of single dye molecules (see scheme) can be followed by confocal fluorescence microscopy. The self-sensitized reaction with singlet oxygen leads to a suite of products, which may be differentiated spectrally. Tentative structures for certain photoproducts have been obtained from quantum-chemical calculations.