scholarly journals Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C1-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes

Polymers ◽  
2018 ◽  
Vol 10 (10) ◽  
pp. 1075 ◽  
Author(s):  
Huajin Wang ◽  
Yanqing Li ◽  
Zhengguo Cai

A C1-symmetric (methylphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (1) and (diphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (2) were synthesized and characterized by 1H NMR, element analysis, and X-ray crystal analysis. The coordination mode of the fluorenyl ligand to the titanium metal is an η3 manner in each complex. These complexes were applied for propylene polymerization using dried modified methyaluminoxane (dMMAO) as a cocatalyst under different propylene pressures in a semi batch-type method. The catalytic activity was strongly dependent on the structure of the complex and the propylene pressure, where complex 1 exhibited the highest activity (600 kg mol−1·h−1) under a propylene pressure of 8.0 atm to produce high molecular weight polypropylene. The polypropylenes obtained were syndiotactic-rich with an rr value of 0.50, indicating that the silylene bridge was not efficient for the isospecificity of a constrained geometry catalyst (CGC). The mechanical properties of the resulting polymers depended on their microstructure.

Author(s):  
G.F. Bastin ◽  
H.J.M. Heijligers ◽  
J.M. Dijkstra

For the calculation of X-ray intensities emitted by elements present in multi-layer systems it is vital to have an accurate knowledge of the x-ray ionization vs. mass-depth (ϕ(ρz)) curves as a function of accelerating voltage and atomic number of films and substrate. Once this knowledge is available the way is open to the analysis of thin films in which both the thicknesses as well as the compositions can usually be determined simultaneously.Our bulk matrix correction “PROZA” with its proven excellent performance for a wide variety of applications (e.g., ultra-light element analysis, extremes in accelerating voltage) has been used as the basis for the development of the software package discussed here. The PROZA program is based on our own modifications of the surface-centred Gaussian ϕ(ρz) model, originally introduced by Packwood and Brown. For its extension towards thin film applications it is required to know how the 4 Gaussian parameters α, β, γ and ϕ(o) for each element in each of the films are affected by the film thickness and the presence of other layers and the substrate.


Author(s):  
John J. Donovan ◽  
Donald A. Snyder ◽  
Mark L. Rivers

We present a simple expression for the quantitative treatment of interference corrections in x-ray analysis. WDS electron probe analysis of standard reference materials illustrate the success of the technique.For the analytical line of wavelength λ of any element A which lies near or on any characteristic line of another element B, the observed x-ray counts at We use to denote x-ray counts excited by element i in matrix j (u=unknown; s=analytical standard; ŝ=interference standard) at the wavelength of the analytical line of A, λA (Fig. 1). Quantitative analysis of A requires an accurate estimate of These counts can be estimated from the ZAF calculated concentration of B in the unknown C,Bu measured counts at λA in an interference standard of known concentration of B (and containing no A), and ZAF correction parameters for the matrices of both the unknown and the interference standard at It can be shown that:


1983 ◽  
Vol 48 (2) ◽  
pp. 586-595 ◽  
Author(s):  
Alexander Perjéssy ◽  
Pavol Hrnčiar ◽  
Ján Šraga

The wave numbers of the fundamental C=O and C=C stretching vibrations, as well as that of the first overtone of C=O stretching vibration of 2-(3-, and 4-substituted phenylmethylene)-1,3-cycloheptanediones and 1,3-cycloheptanedione were measured in tetrachloromethane and chloroform. The spectral data were correlated with σ+ constants of substituents attached to phenyl group and with wave number shifts of the C=O stretching vibration of substituted acetophenones. The slope of the linear dependence ν vs ν+ of the C=C stretching vibration of the ethylenic group was found to be more than two times higher than that of the analogous correlation of the C=O stretching vibration. Positive values of anharmonicity for asymmetric C=O stretching vibration can be considered as an evidence of the vibrational coupling in a cyclic 1,3-dicarbonyl system similarly, as with derivatives of 1,3-indanedione. The relationship between the wave numbers of the symmetric and asymmetric C=O stretching vibrations indicates that the effect of structure upon both vibrations is symmetric. The vibrational coupling in 1,3-cycloheptanediones and the application of Seth-Paul-Van-Duyse equation is discussed in relation to analogous results obtained for other cyclic 1,3-dicarbonyl compounds.


Author(s):  
Radosław Rogoziński ◽  
Alina Maciejewska

AbstractVarved clay deposits from ice-dammed lakes are a particularly important and broadly applied raw material used for the production of high-quality ceramics (red bricks, roof tiles, etc.), but the mineralogy and geochemistry of these sediments are not fully understood. The aim of the present study was to determine the chemical and mineralogical composition of ice-dammed lake sediments of the Lębork deposit. Major-element analysis of the compositions of selected samples from the ice-dammed lake clays was performed by X-ray fluorescence (XRF) and trace elements were determined by inductively coupled plasma-mass spectrometry. The mineralogical composition of clay samples was determined by X-ray diffraction (XRD). Analyses of the chemical composition of the ice-dammed lake clays of the Lębork deposit showed that the dominant component was SiO2 with a mean content of 56.13 wt.%; the second most abundant component was Al2O3, with a mean content for the entire deposit of 11.61 wt.%. Analysis by ICP-MS indicated the presence of rare earth elements (REE), e.g. cerium, neodymium, lanthanum, and praseodymium; their mean contents are: 56.9, 27.0, 26.3, and 7.3 ppm, respectively. Mineralogical analysis of the varved clays identified quartz, muscovite, calcite, and clay minerals – illite, kaolinite, and montmorillonite. The material filling the Lębork basin is characterized by small lateral and vertical variability in chemical composition. The results of the present study may be of considerable importance in determining the parent igneous, metamorphic, and sedimentary rocks, the weathering products of which supplied material to the ice-dammed lake, as well as in determining the mechanisms and character of the sedimentation process itself.


1995 ◽  
Vol 39 ◽  
pp. 109-117
Author(s):  
Burkhard Beckhoff ◽  
Birgit Kanngießer

X-ray focusing based on Bragg reflection at curved crystals allows collection of a large solid angle of incident radiation, monochromatization of this radiation, and condensation of the beam reflected at the crystal into a small spatial cross-section in a pre-selected focal plane. Thus, for the Bragg reflected radiation, one can achieve higher intensities than for the radiation passing directly to the same small area in the focal plane. In that case one can profit considerably from X-ray focusing in an EDXRF arrangement. The 00 2 reflection at Highly Oriented Pyrolytic Graphite (HOPG) crystals offers a very high intensity of the Bragg reflected beam for a wide range of photon energies. Furthermore, curvature radii smaller than 10 mm can be achieved for HOPG crystals ensuring efficient X-ray focusing in EDXRF applications. For the trace analysis of very small amounts of specimen material deposited on small areas of thin-filter backings, HOPG based X-ray focusing may be used to achieve a very high intensity of monochromatic excitation radiation.


2003 ◽  
Vol 56 (12) ◽  
pp. 1187 ◽  
Author(s):  
Paul V. Bernhardt ◽  
Tri Erny Dyahningtyas ◽  
Jack M. Harrowfield ◽  
Jee-Young Kim ◽  
Yang Kim ◽  
...  

Chiral resolution of the cobalt cage complexes [Co(diNOsar)]3+ and [Co(diAMsarH2)]5+ have been achieved by selective crystallization with the anion bis-μ-(R), (R)-tartratodiantimonate(III) ([Sb2(R,R-tart)2]2–) and also by column chromatography with Na2[Sb2(R,R-tart)2] as eluent. The X-ray crystal structures of Λ-[Co(diNOsar)][Sb2(R,R-tart)2]Cl . 7 H2O and Δ-[Co(diAMsarH2)][Sb2(R,R-tart)2]2Cl . 14 H2O are reported, which reveal an unexpected reversal of chiral discrimination when the cage substituent is changed from nitro (Λ-enantiomer) to ammonio Δ-enantiomer) and shows that the ammonio-substituted cage is capable of forming a three-point hydrogen-bonding interaction with each complex anion, whereas the nitro analogue can only form two hydrogen bonds with each [Sb2(R,R-tart)2]2– anion. During cation exchange chromatography of the racemic cobalt cage complexes with Na2[Sb2(R,R-tart)2] as eluent, Λ-[Co(diNOsar)]3+ elutes first, which implies a tighter ion pairing interaction than for the Δ-enantiomer. On the other hand, Δ-[Co(diAMsarH2)]5+ elutes first during chromatography under identical conditions, which is also consistent with a preferred outer-sphere complex formed between Δ-[Co(diAMsarH2)]5+ and [Sb2(R,R-tart)2]2– relative to Λ-[Co(diAMsarH2)]5+ and [Sb2(R,R-tart)2]2–.


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