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991.
Pyrolytic hydrolysis of polycarbonate in the presence of earth-alkali oxides and hydroxides 总被引:1,自引:0,他引:1
Guido Grause 《Polymer Degradation and Stability》2009,94(7):1119-1124
The rise in the use of polycarbonate (PC) calls for the development of after-use treatments. In this work, we describe a process for obtaining bisphenol A (BPA), phenol and isopropenyl phenol (IPP) from PC by hydrolysis at temperatures between 300 and 500 °C. The experiments were carried out in a steam atmosphere in the presence of MgO, CaO, Mg(OH)2 or Ca(OH)2 as catalysts, respectively. The results were compared with the hydrolysis of PC in the absence of any catalysts. All of these catalysts accelerated the hydrolysis of PC drastically, with MgO and Mg(OH)2 being more effective than their Ca counterparts. The differences between oxides and hydroxides were negligible indicating the same mechanism for both, oxides and hydroxides. BPA was the main product at 300 °C, with a yield of 78% obtained in the presence of MgO. At 500 °C, BPA was mainly degraded to phenol and isopropenyl phenol (IPP). It can be shown that a combined process involving PC hydrolysis at 300 °C and BPA fission at 500 °C leads to high yields of phenol and IPP and the drastic decrease of residue. 相似文献
992.
Denis Veynante Guido Lodato Pascale Domingo Luc Vervisch Evatt R. Hawkes 《Experiments in fluids》2010,49(1):267-278
Turbulence motions are, by nature, three-dimensional while planar imaging techniques, widely used in turbulent combustion, give only access to two-dimensional information. For example, to extract flame surface densities, a key ingredient of some turbulent combustion models, from planar images implicitly assumes an instantaneously two-dimensional flow, neglecting the unresolved flame front wrinkling. The objective here is to estimate flame surface densities from two-dimensional measurements assuming that (1) the flow is statistically two dimensional; (2) the measuring plane is a plane of symmetry of the mean flow, either by translation (homogeneous third direction as in slot burners for example) or by rotation (axi-symmetrical flows such as jets) and (3) flame movements in transverse directions are similar. The unknown flame front wrinkling is then modelled from known quantities. An excellent agreement is achieved against direct numerical simulation (DNS) data where all three-dimensional quantities are known, but validations in other conditions (larger DNS, experiments) are required. 相似文献
993.
Chao He Guido Kuenne Esra Yildar Jeroen van Oijen Francesca di Mare Amsini Sadiki 《Combustion Theory and Modelling》2017,21(6):1080-1113
This work shows experiments and simulations of the fired operation of a spark ignition engine with port-fuelled injection. The test rig considered is an optically accessible single cylinder engine specifically designed at TU Darmstadt for the detailed investigation of in-cylinder processes and model validation. The engine was operated under lean conditions using iso-octane as a substitute for gasoline. Experiments have been conducted to provide a sound database of the combustion process. A planar flame imaging technique has been applied within the swirl- and tumble-planes to provide statistical information on the combustion process to complement a pressure-based comparison between simulation and experiments. This data is then analysed and used to assess the large eddy simulation performed within this work. For the simulation, the engine code KIVA has been extended by the dynamically thickened flame model combined with chemistry reduction by means of pressure dependent tabulation. Sixty cycles have been simulated to perform a statistical evaluation. Based on a detailed comparison with the experimental data, a systematic study has been conducted to obtain insight into the most crucial modelling uncertainties. 相似文献
994.
Manuela M. Moreira Luís F. Guido José M. Cruz Aquiles A. Barros 《Central European Journal of Chemistry》2010,8(6):1236-1243
A reversed-phase high-performance liquid chromatographic (HPLC) method is applied for the determination of galacturonic acid
(GA) of pectins in different commercial fruit juices. The separation was carried out on a C18 column using precolumn derivatization with p-aminobenzoic acid (p-ABA) and UV detection at 304 nm. The identification of GA was confirmed by high-performance liquid chromatography/electrospray
ionization tandem mass spectrometry (HPLC-ESI-MS/MS) in positive ion mode. The concentration of GA in the samples analyzed
ranged from 12.9 ± 0.5 to 49.4 ± 0.5 mgGA L−1. Amongst the samples analyzed, mango juice was found to be richest in GA content, and therefore a good source of pectins.
Detection and quantification limits of the described methodology were 1.2 and 3.9 mg L−1, respectively. Quantitative GA recoveries in the beverages had a range between 90 and 98%. The results showed that the HPLC
method proposed was precise and suitable for the identification and quantification of GA in commercial fruit juices. 相似文献
995.
For two contacting rigid bodies, the friction force F is proportional to the normal load and independent of the macroscopic contact area and relative velocity V (Amonton's law). With two mutually sliding polymer samples, the surface irregularities transmit deformation to the underlying material. Energy loss along the deformation cycles is responsible for the friction force, which now appears to depend strongly on V [see, e.g., N. Maeda et al., Science 297, 379 (2002)]. We base our theoretical interpretation on the assumption that polymer chains are mainly subjected to oscillatory "reptation" along their "tubes." At high deformation frequencies-i.e., with a large sliding velocity V-the internal viscosity due to the rotational energy barriers around chain bonds hinders intramolecular mobility. As a result, energy dissipation and the correlated friction force strongly diminish at large V. Derived from a linear differential equation for chain dynamics, our results are basically consistent with the experimental data by Maeda et al. [Science 297, 379 (2002)] on modified polystyrene. Although the bulk polymer is below T(g), we regard the first few chain layers below the surface to be in the liquid state. In particular, the observed maximum of F vs V is consistent with physically reasonable values of the molecular parameters. As a general result, the ratio FV is a steadily decreasing function of V, tending to V(-2) for large velocities. We evaluate a much smaller friction for a cross-linked polymer under the assumption that the junctions are effectively immobile, also in agreement with the experimental results of Maeda et al. [Science 297, 379 (2002)]. 相似文献
996.
González-Pérez JM Alarcón-Payer C Castiñeiras A Pivetta T Lezama L Choquesillo-Lazarte D Crisponi G Niclós-Gutiérrez J 《Inorganic chemistry》2006,45(2):877-882
The windmill-shaped hexanuclear copper(II) cluster {(H(2)O)(2)Cu(2)(mu(3)-(Ade)(4)[Cu(oda)(H(2)O)](4)}.6H(2)O (1-o) has been synthesized in aqueous medium by in situ core-controlled expansion of the neutral building block Cu(2)(mu(2)-N3,N9-Ade)(4)(H(2)O)(2) (2) with Cu(oda)(H(2)O) (3-o) (Ade = adeninato(1-) and oda = oxydiacetato(2-) ligands). Crystal data for 2-b (2.5H(2)O): triclinic, space group P(-)1; a = 9.374(1), b = 9.440(1), c = 10.326(1) A; alpha = 78.72(1), beta = 76.77(1), gamma = 63.51(1) degrees ; final R(1) = 0.059; T = 100(2) K. Crystal data for 1-o: monoclinic, space group P2(1)/n; a = 15.203(2), b = 10.245(1), c = 19.094(2) A; beta = 101.61(1) degrees ; final R(1) = 0.049; T = 293(2) K. The X-shaped hexanuclear molecule consists of a central core (2) and four terminal arms (3-o) linked together by bridging mu(3)-N3,N7,N9-Ade ligands. There are three crystallographic independent metal atoms (two terminals, one central). All Cu(II) atoms exhibit a 4 + 1 coordination, of which one is an aqua apical ligand. The basal coordination sets complete the CuN(4) + O or CuO(3)N + O chromophores for the central or terminal metal atoms, respectively. Thermal stability and spectral and magnetic properties were also studied. Analogous compounds to 1-o with tridentate or tripodal tetradentate ligands L(2-), instead of oda, have also been synthesized. 相似文献
997.
Gais HJ Kramp GJ Wolters D Reddy LR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(21):5610-5617
We describe new fully stereocontrolled syntheses of the prostacyclin analogues iloprost (2), the most active component of the drugs Ilomedin and Ventavis, and 3-oxa-iloprost (3), a derivative that is expected to have a significantly higher metabolic stability than 2 perhaps allowing an oral application. The syntheses are based on the same strategy and chiral bicyclic building block as used in the synthesis of cicaprost (4), the third most potent analogue that exhibits, besides prostacyclin-like activities, antimetastatic activities. Reaction of the enantiopure C6-C13 bicyclic aldehyde 17 with Cl(3)CCOOH/Cl(3)CCOONa afforded trichlorocarbinol 24 which was converted via mesylate 25 to the C6-C14 bicyclic alkyne 9. The palladium-catalysed hydrostannylation of alkyne 9 gave with high regio- and stereoselectivity the alkenylstannane 26, Sn/Li exchange of which afforded the E-configured alkenyllithium derivative 8. Coupling of the C6-C14 building block 8 with the enantiopure C15-C20 building block, the N-methoxyamide 7, gave the C6-C20 bicyclic ketone 6 in high yield without epimerisation at C16. The configuration at C15 of iloprost (2) and 3-oxa-iloprost (3) was established through a highly diastereoselective reduction of ketone 6 with catecholborane and the chiral oxazaborolidine 28 which furnished alcohol (15S)-29. The highly stereoselective conversions of alcohol (15S)-29 to iloprost (2) and 3-oxa-iloprost (3), which include as key stereoselective steps an olefination with a chiral phosphonoacetate and a copper-mediated allylic alkylation, have already been described. 相似文献
998.
999.
The economic cycle of aluminium is a didactical concept both for school and university. The student laboratory project presented allows the concrete implementation. Based on the simultaneous education between industry and didactics of chemistry is the illustrated teacher education. This concept is easily transferable to other topics, so that school, university and industry can interact more often with each other. 相似文献
1000.
We justify the validity of the discrete nonlinear Schrödinger equation for the tight-binding approximation in the context of the Gross-Pitaevskii equation with a periodic potential. Both piecewise-constant and smooth potentials are considered in the semi-classical limit. While justification of stationary equations is developed in our previous work (Pelinovsky et al. (2008) [11]), this work deals with time-dependent space-decaying solutions on large but finite time intervals. 相似文献