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61.
Tatiana B. Mikenas Vladimir A. Zakharov Lyudmila G. Echevskaya Mikhail A. Matsko 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5057-5066
The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl2/MgCl2‐Al(i‐Bu)3 (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl2/MgCl2‐Al(i‐Bu)3 has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl2/MgCl2‐Al(i‐Bu)3 has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007 相似文献
62.
Ke Sha Dongshuang Li Yapeng Li Xiaotian Liu Shuwei Wang Jingqi Guan Jingyuan Wang 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5037-5049
Amphiphilic diblock copolymer polycaprolactone‐block‐poly(glycidyl methacrylate) (PCL‐b‐PGMA) was synthesized via enzymatic ring‐opening polymerization (eROP) and atom transfer radical polymerization (ATRP). Methanol first initiated eROP of ?‐caprolactone (?‐CL) in the presence of biocatalyst Novozyme‐435 under anhydrous conditions. The resulting monohydroxyl‐terminated polycaprolactone (PCL–OH) was subsequently converted to a bromine‐ended macroinitiator (PCL–Br) for ATRP by esterification with α‐bromopropionyl bromide. PCL‐b‐PGMA diblock copolymers were synthesized in a subsequent ATRP of glycidyl methacrylate (GMA). A kinetic analysis of ATRP indicated a living/controlled radical process. The macromolecular structures were characterized for PCL–OH, PCL–Br, and the block copolymers by means of nuclear magnetic resonance, gel permeation chromatography, and infrared spectroscopy. Differential scanning calorimetry and wide‐angle X‐ray diffraction analyses indicated that the copolymer composition (?‐CL/GMA) had a great influence on the thermal properties. The well‐defined, amphiphilic diblock copolymer PCL‐b‐PGMA self‐assembled into nanoscale micelles in aqueous solutions, as investigated by dynamic light scattering and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5037–5049, 2007 相似文献
63.
Xiao‐Hui Liu Yan‐Guo Li Ying Lin Yue‐Sheng Li 《Journal of polymer science. Part A, Polymer chemistry》2007,45(7):1272-1281
The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. 1H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 2007 相似文献
64.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(27):7007-7007
65.
The trisilanol 1,3,5‐(HOi‐Bu2Si)3C6H3 ( 7 ), prepared in three steps from 1,3,5‐tribromobenzene via the intermediates 1,3,5‐(Hi‐Bu2Si)3C6H3 ( 8 ) and 1,3,5‐(Cli‐Bu2Si)3C6H3 ( 9 ) forms an equimolar complex with trans‐bis(4‐pyridyl)ethylene (bpe), 7 ·bpe, whose structure was investigated by X‐ray crystallography. The hydrogen‐bonded network features a number of SiO? H(H)Si and SiO? H hydrogen bridges. Evidence was found for cooperative strengthening within the sequential hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
66.
Praveen K. Tandon Gayatri Sumita Sahgal Manish Srivastava Santosh B. Singh 《应用有机金属化学》2007,21(3):135-138
Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H2O2. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
67.
Applied Biochemistry and Biotechnology - 相似文献
68.
Arabinda Mallick 《Journal of luminescence》2006,118(2):165-172
Solvatochromic effects on the fluorescence behavior of 7-hydroxy-4-methyl-8-(4′-methyl-piperazine-1′ yl)methylcoumarin (HMMC) was studied in different solvents. The fluorescence of HMMC was found to be highly sensitive to both the polarity and the protic character of the solvent. Exploiting the polarity-sensitive fluorescence property of HMMC, its excited-state dipole moment has been determined. Fluorescence (Förster) resonance energy transfer (FRET) process from HMMC to a potent bioactive molecule 3-acetyl-4-oxo-6,7-dihydro-12 H indolo-[2,3-a] quinolizine (AODIQ) was studied. From the determined KSV and R0 values, it is argued that a long-range dipole-dipole interaction is operating for the energy transfer mechanism. The energy transfer efficiency (E) and the distance between the acceptor and the donor (r0) have been determined. 相似文献
69.
We have studied the characteristic features of carbazole phosphorescence quenching by benzophenone in toluene at 77 K. We
have shown that the decrease in the relative phosphorescence intensity for carbazole (energy donor) by a greater factor than
we see for the relative change in its decay time is due to the fact that a change in the phosphorescence decay time occurs
only for carbazole molecules participating in triplet-triplet energy transfer, while the substantial decrease in the phosphorescence
intensity for carbazole with no change in the phosphorescence decay time is connected with quenching of its singlet states.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 554–556, July–August, 2006. 相似文献
70.
A control volume type numerical methodology for the analysis of steady three‐dimensional rotating flows with heat transfer, in both laminar and turbulent conditions, is implemented and experimentally tested. Non‐axisymmetric momentum and heat transfer phenomena are allowed for. Turbulent transport is alternatively represented through three existing versions of the k–ε model that were adjusted to take into account the turbulence anisotropy promoted by rotation, streamline curvature and thermal buoyancy. Their relative performance is evaluated by comparison of calculated local and global heat balances with those obtained through measurements in a laboratory device. A modified version of the Lam and Bremhorst, low Reynolds number model is seen to give the best results. A preliminary analysis focused on the flow structure and the transfer of heat is reported. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献