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排序方式: 共有254条查询结果,搜索用时 15 毫秒
1.
A. Razavi V. Bellia D. Baekelmans M. Slawinsky S. Sirol L. Peters Ulf Thewalt 《Kinetics and Catalysis》2006,47(2):257-267
In this contribution, the stereochemistry of propylene insertion/propagation reactions with a variety of C
1 symmetric metallocene catalysts, containing bridged cyclopentadienyl-fluorenyl ligand for the preparation of highly stereoregular
polypropylene is presented. The impact of the distal substitutent’s size and composition and changes that the catalytic sites
undergo upon such substitution is elaborated. A comprehensive mechanism is proposed to explain the resulting catalytic changes
that bring about the irreversible C
s/C
1 site transformation and tactic behavior inversion. Furthermore the cyclopentadienyl’s combined distal/proximal and fluorenyl’s
frontal substituent effects on molecular weight, regio-, and stereoregularity of the final polymers are discussed. Finally,
stereoselectivities of C
2 and C
1 symmetric catalyst systems are compared. It is shown that current high performance C
1 symmetric catalyst systems with central site chirality can be isotactic selective as well or even better in certain aspects
than the C
2 symmetric bridged bisindenyl-based metallocene catalysts.
The text was submitted by the authors in English. 相似文献
2.
3.
James C. W. Chien Abbas Razavi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(9):2369-2380
Bis(neomenthyl cyclopentadienyl)zirconium dichloride/methyl aluminoxane (η5-(NMCp)2ZrCl2/MAO) catalyst has been investigated for ethylene polymerization. About 51% of the Zr forms active sites more or less instantaneously according to quenching with tritiated methanol. There is an initial drop of rate of polymerization, Rp, of about 30% which remains constant thereafter. The catalytic activity increases monotonically with temperature; it is proportional to [MAO]1.75 at a constant [Zr] = 1.5 μM and proportional to [Zr]?1.2 at a constant [MAO] = 64.5 mM. At very large [MAO]/[Zr], the catalyst has extremely high activity; κp = 5 × 103 (Ms)?1 at 50°C. There is also facile chain transfer to aluminum, κ = 0.14 s?1 at 50°C. Both κp and κ are about 30 times greater than the corresponding rate constants for MgCl2 supported TiCl3 catalysts. The TiCl3/MgCl2 and (NMCp)2/MAO catalysts have nearly the same activation energy for propagation (ca. 7 kcal/mol?1). The higher activity of the latter is due to its larger preexponential factor in κp. The dependence of catalytic activity on the [MAO]/[Zr] ratio may be explained by rapid association-dissociation equilibria of MAO involving acid-base and/or electron deficient bridge complexation. 相似文献
4.
Fe3O4@SiO2@propyltriethoxysilane@o‐phenylendiamine as an environmentally‐benign functionalized silica‐coated magnetic organometallic nanomaterial has been synthesized and characterized by Fourier transforms infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM) images and energy dispersive X‐ray (EDX) and vibrating sample magnetometer (VSM) analyses. Then, its catalytic activity was investigated for the one‐pot three‐component condensation reaction between dimedone, malononitrile and various substituted aromatic aldehydes to afford the corresponding 2‐amino‐4H‐chromene derivatives under mild reaction conditions. This nanocatalyst can be easily recovered from the reaction mixture by using a magnet and reused for at least five times without significant decrease in catalytic activity. 相似文献
5.
6.
Razieh Fazaeli Hamid Aliyan Elham Naderi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6):745-754
Abstract The immobilization of heteropoly acids (HPAs) into the Al-functionalized KIT-6 mesoporous molecular sieve has been carried out to see the effect of Al-KIT-6 as a host matrix on the HPA activities. These modified mesoporous molecular sieves are effective catalysts for the Hosomi–Sakurai three-component coupling reaction via condensation of aldehydes, silyl ethers, and allylsilanes. Supplemental materials are available for this paper. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
7.
Sahra Balilehvand Seyed Majid Hashemianzadeh SeyedehSaleheh Razavi Hedayat Karimi 《Adsorption》2012,18(1):13-22
A combination of ab initio quantum mechanical (QM) calculations and canonical Monte Carlo (CMC) simulations are employed to
investigate possible usage of single-walled silicon nanotubes (SWSiNTs) as a novel media for hydrogen and methane adsorption
as well as their separation from each other. By fitting the force field, a Morse potential model is selected as an efficient
potential to describe the binding energies between both hydrogen-SiNTs and methane-SiNTs obtained from ab initio calculations.
Then CMC simulations are performed to evaluate the adsorption and separation behaviors of H2 and CH4 on the three different sizes of SiNTs including (5, 5), (7, 7), and (9, 9) SiNTs at ambient temperatures and pressures from
1 up to 10 MPa. As a comparison, the adsorption and separation of H2 and CH4 on the (8, 8) CNTs which are isodiameter with (5, 5) SiNTs are also simulated. Results are indicative of remarkable enhancement
of H2 and CH4 adsorption capacity on the SiNTs compared to the CNTs, which arise from stronger van der Waals (VDW) attractions. In the
case of methane adsorption on SiNTs, the stored volumetric energy exceeds the goal of the US Freedom CAR Partnership by 2010,
which can not be achieved by methane compression at such low pressures. Moreover, simulation results indicate that SiNTs preferentially
adsorb methane relative to hydrogen in their equimolar mixture, which results in efficient separation of these gases from
each other at 293 K. 相似文献
8.
A new characteristic approach for incompressible thermo‐flow in Cartesian and non‐Cartesian grids
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A virtual‐characteristic approach is developed for thermo‐flow with finite‐volume methodology in which a multidimensional characteristic (MC) scheme is applied along with artificial compressibility. To obtain compatibility equations and pseudo‐characteristics, energy equation is taken into account in the MC scheme. With this inherent upwinding of convective fluxes, no artificial viscosity is required even at high Reynolds numbers. Another remarkable advantage of the MC scheme lies in its faster convergence rate with respect to the averaging scheme that is found to exhibit substantial delays in convergence. As benchmarks, forced and mixed convections in a cavity and in flow over cylinder and between parallel plates are examined for a wide range of Reynolds, Grashof, and Prandtl numbers. The MC and averaging schemes are applied for simulation purposes. Results show the better performance of the MC scheme in forced and mixed convections. Results confirm the robustness of the MC scheme in terms of accuracy and convergence. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
9.
Razieh Doostmohammadi Malek Taher Maghsoodlou Nourallah Hazeri Sayyed Mostafa Habibi-Khorassani 《中国化学快报》2013,24(10):901-903
A facile one-pot synthesis of 3,4,5-substituted furan-2(5H)-one derivatives from a three-component reaction of aniline derivatives, dialkylacetylenedicarboxylates and aromatic aldehydes under mild conditions using tetra-n-butylammonium bisulfate as a catalyst has been developed. 相似文献
10.