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91.
Oxidative addition of methyl iodide to Vaska’s complex in the ionic liquids 1-butyl-3-methylimidazolium triflate [C4mim][OTf], [C4mim] bis(trifluormethylsulfonyl)imide [Tf2N], and N-hexylpyridinium [C6pyr][Tf2N] occurred cleanly to give the expected Ir(III) oxidative addition product. Pseudo-first order rate constants were determined for the oxidative addition reaction in each solvent ([Vaska’s] = 0.25 mM, [CH3I] = 37.5 mM). The observed rate constants under these conditions were 5-10 times slower than the rate seen in DMF. At high methyl iodide concentrations (>23 mM), the expected first order dependence on methyl iodide was not observed. In each ionic liquid, there was no change in the reaction rates within experimental error over the methyl iodide concentration range of 23-75 mM. At lower methyl iodide concentration, a decrease in rate was observed in [C4mim][Tf2N] with decreasing concentration of methyl iodide.  相似文献   
92.
This paper gives the equilibrium distribution of polymer sizes for Flory'sA g RB f–g model of polymerization. In this model, the polymers are composed of structural units withg functional groups of the typeA and (f-g) functional groups of the typeB. Reaction is subject to three conditions: (1) Functional groups of the typeA react only with those of typeB, and vice versa. (2) Intramolecular reactions do not occur [and therefore only branched-chain (noncyclic) polymers and formed]. (3) Subject to conditions (1) and (2), all functional groups are equally reactive. The derivation employs Stockmayer's statistical mechanical method (first used on Flory'sRA f model), coupled with a recursion giving the number of distinct polymers which may be assembled fromk units of theA g RB f–g type. We also give distributions for a limiting case of theA g RB f–g model, the so-calledA g RB model. This paper completes the solution of the Smoluchowski coagulation equation (monodisperse case) for the kernelsa ij =A + B(i +j)+ Cij. The proof will be given in another publication.  相似文献   
93.
碱金属改性Y分子筛的甲苯氧化甲基化反应性能及其酸碱性质*周灵萍李伟苏明李赫口亘陶克毅**(南开大学化学系,天津300071)关键词Y型分子筛,甲苯,甲烷,氧化甲基化,苯乙烯,乙苯,酸性,碱性分类号O643/TQ42苯乙烯和乙苯是重要的化工原料.以往合...  相似文献   
94.
The kinetics of liquid crystalline copolyester synthesis via melt transesterification between poly(butylene terephthalate) (PBT), terephthalic acid (TA) and hydroquinone diacetate (HQDA) is examined. Two different copolyester compositions PBT30/(HQDA+TA) 70 and PBT 50/(HQDA+TA) 50 mol% ratio were synthesized. The ratio of HQDA to TA was kept constant for all the reactions.The copolyesters were synthesized via melt polycondensation route at 265°C, 275°C and 285°C using two different transesterification catalysts, zinc acetate and dibutyl tin oxide. A key postulation assumed in this work is that the reaction originates between TA and HQDA to form a dimer which slices PBT chain. The copolyesterification rate constant for a system containing butylene glycol a more nonpolar moiety compared to ethylene glycol in poly(ethylene terephthalate) has been determined. The activation energy values for the different copolymer systems has also been determined. The rate constants for the uncatalyzed and catalyzed copolyesterification reaction and the activation energy values for the reaction have been determined.  相似文献   
95.
新型尼龙214,414,614,814,1014和1214的合成与表征   总被引:3,自引:0,他引:3  
张国胜  李勇进  颜德岳 《化学学报》2002,60(11):2078-2082
用熔融缩聚法基于十四碳二酸合成了一系列偶偶尼龙,包括尼龙2 14,4 14, 6 14,8 14,10 14,12 14。用红外光谱、元素分析、核磁共振、差示扫描热分析 、热失重分析、热机械分析、粘度法对合成尼龙的结构与性能进行了表征。同时还 初步研究了尼龙12 14的物理性能,发现其物理性能介于尼龙66和聚乙烯之间。  相似文献   
96.
Polyurea microcapsules about 2.5μm in diameter containing phase change material for thermal energy storage application were synthesized and characterized by interfacial polycondensation method with toluene-2,4-diisocyanate and ethylenediamine as monomers in an emulsion system. Hexadecane was used as a phase change material and OP, which is nonionic surfactant, and used as an emulsifier. The chemical structure and thermal behavior of the microcapsules were investigated by FTIR and thermal analysis respectively. The results show encapsulated hexadecane has a good potential as a solar energy storage material.  相似文献   
97.
Poly(propylene adipate) (PPA) and poly(propylene isophthalate/adipate) (PPI-PPA) random copolymers of various compositions were synthesized in bulk and characterized in terms of chemical structure and molecular weight. Furthermore, the thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers showed a good thermal stability. At room temperature they appeared as semicrystalline materials, except the copolymers containing 20 and 30 mol% of PI units: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. The crystalline phase of PPI and PPA was evidenced at high content of propylene isophthalate or propylene adipate units, respectively. Amorphous samples were obtained after melt quenching and an increment of Tg as the content of PI units is increased was observed. This behavior was explained as due to the stiff phenylene groups in the polymeric chain. The Wood equation was found to describe well Tg-composition data. Lastly, the presence of a rigid-amorphous phase was evidenced in the copolymers, differently from PPA homopolymer.  相似文献   
98.
The elucidation of structures of glutathione (GSH) complexes play an important role in the fundamental understanding of biochemical pathways of metal ion deactivation in plants. This article attempts to feature key studies for stoichiometry of metal complexes with glutathione and its constituent amino acids to obtain a better understanding of the different metal affinities of the complexation sites of glutathione. The SEC-ICP-MS experiments have indicated that oxidation process of glutathione was accelerated by metal ion presence in following order Cu+, Pb2+ and Cd2+. The redox activity of metal ions was confirmed by ESI-MS experiments, which allowed to observe formation of glutathione disulphide (GSSG) in time. The stoichiometry of Cd2+, Cu+ and Pb2+ complexes with GSH was defined by observing the isotope pattern of investigated metals and hydrogen loss or transfer during binding. The complexes with metal bound to sulphur of 1:1 and 1:2 stoichiometry were found in case of cadmium and lead. The number of hydrogen atoms lost during metal binding and the SEC-ESI-MS results allowed to elucidate that copper is bound by GSSG in ratio 1:1 and 1:2. Additionally, size exclusion chromatography coupled to electrospray MS allowed to differentiate more stable complexes from weak ones that could be created in the gas phase.  相似文献   
99.
4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by 1H‐NMR, 19F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   
100.
Loss of diamine and distinct transition phenomena from the solid to the melt state restrain solid-state polymerization (SSP) of nylon salts from industrial application. To depress these phenomena temperatures well below the melting point of the starting material are employed, resulting however in low reaction rates. The need to use catalysts arises and accordingly in this study hexamethylenediammonium adipate (HMA) particles were polymerized containing a strictly controlled amount of uniformly distributed catalyst. The catalysts included boric, sulphuric, and phosphoric acids with boric acid being the most effective in accelerating the reaction while eliminating the tendency to agglomeration. In general, catalyst concentration up to a critical value plays a considerable role in the overall behavior. Furthermore, in agreement with non catalytic processes, the reaction temperature remains an influential parameter. © 1994 John Wiley & Sons, Inc.  相似文献   
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