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21.
Glenn Gillies Daniel Dönnecke Wolfgang Imhof 《Monatshefte für Chemie / Chemical Monthly》2007,138(7):683-686
Summary. The reaction of the unsaturated imine methyl(3-phenylallylidene)amine with ethylene and carbon monoxide in the presence of
catalytical amounts of Ru3(CO)12 leads to the formation of two heterocyclic products. One of the products is a chiral γ-lactam, the other one a 2,3-disubstituted
pyrrole derivative, in which only the carbon atom from carbon monoxide is incorporated. The selectivity in the formation of
the products may be controlled by the choice of solvent. In general, in nonpolar solvents the formation of the lactam is preferred
whereas the use of more polar solvents enhances the yield of the pyrrole. For most of the solvents used there is a linear
dependence of the product ratio on the relative permittivity of the corresponding solvent. Typically, polar aprotic solvents
do not follow this rule. 相似文献
22.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
23.
Study on flame-retardant mechanism of polycarbonate containing sulfonate-silsesquioxane-fluoro retardants by TGA and FTIR 总被引:1,自引:0,他引:1
Shumei Liu Yongsheng Zhou Zhijie Jiang Xianbo Huang 《Polymer Degradation and Stability》2006,91(8):1808-1814
The flame retardancy of bisphenol A polycarbonate (PC) containing potassium diphenylsulfone sulfonate (KSS), poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) and poly(vinylidenefluoride) (PVDF) was measured by limited oxygen index (LOI) and examined according to UL94. A high LOI and UL94 V-0 rating for 1.6 mm thickness samples were obtained by a combined use of equivalent KSS, PAPSQ and PVDF at 0.1-0.3 wt% loading, respectively. The improvement in flame retardancy of PC compositions arose from the synergistic interaction of three additives. Thermogravimetric analysis (TGA) indicated that the combination decreased the activation energy (E) of PC degradation and elevated the thermal degradation rate of PC to ensure the formation of an insulating carbon layer. FTIR analysis showed that the LOI char of PC containing the three additives took on a highly cross-linking aromatic ester and ether structure. 相似文献
24.
25.
Solid-state kinetics was developed from kinetic concepts for reactions in homogeneous phase systems, which has created considerable debate over issues such as variable activation energy. This behavior has been viewed by some as a violation of basic chemical kinetic principles. Variation in activation energy has been detected by isoconversional or ‘model-free’ calculation methods. The relationship between different calculation methods and the occurrence of variable activation energy was investigated in this work by employing model-fitting and isoconversional methods to analyze simulated isothermal data. In addition, these approaches were applied for sulfameter-dioxolane solvate desolvation data. We showed that variable activation energy is of two types—a true variation that results from the complex nature of the solid-state process and an artifactual one resulting from the use of some isoconversional methods. 相似文献
26.
先在0.5 mol·L-1硝酸介质中活化氟离子选择性电极,再在含硝酸的总离子强度调节混合液(TISAM)中测定氟,线性范围为1×10-7~1×10-2mol·L-1,检出限为1.9μg·L-1。该方法应用于绿茶饮料、水、牛奶中痕量氟的测定,结果的RSD小于4.8%,回收率在96.1%至100.2%之间,对氟离子选择性电极在硝酸介质中的活化机理作了阐述。 相似文献
27.
P. Baltazar V. H. Lara G. Córdoba R. Arroyo 《Journal of Sol-Gel Science and Technology》2006,37(2):129-133
Samples of TiO2 doped with 2 and 5 mol% of Cu2+ were prepared by the sol-gel process. Titanium(IV) isopropoxide and copper(II) nitrate were used as precursors. The samples
were prepared as monolithic shapes, dried at 80°C for 72 h and heat treated at various temperatures in the range 200–900°C
for 2 h. The structural transformation and texture of the samples were investigated by X-ray powder diffraction (XRD) and
nitrogen adsorption. Significant changes were observed during the crystallization process; on the one hand, the crystallization
profiles show that crystallization occurs uniformly and is practically insensitive to the dopant concentration, but when the
transformation at a given temperature is followed as a function of time, the rate of the amorphous-anatase transformation
is larger for the sample containing 2 mol% Cu2+. Electron spin resonance (ESR) results show that in this sample there is no segregation of Cu2+ ions. The sample containing 2 mol% of Cu2+ was selected for the kinetic studies and the temperatures selected were 300, 325, 350, 375 and 400°C, which were taken from
the amorphous to anatase crystallization profile. An activation energy of 137 ± 4 kJ/mol for the crystallization process was
estimated from the kinetic data. These results showed that the effect of the open structure present in the TiO2 amorphous phase provides the atomic mobility required for the crystallization. On the other hand, the differences in the
crystallization rate due to the amount of Cu2+ were explained by the segregation of copper ions to the surface of the samples. 相似文献
28.
The first example of an organic reduction with boranes catalyzed by a high valent oxo-complex is reported. The systems catecholborane/MoO2Cl2(H2O)2 (5 mol %) and BH3·THF/MoO2Cl2 (5 mol %) proved to be very efficient for the reduction of sulfoxides to the corresponding sulfides in excellent yields. 相似文献
29.
用化学还原法制备了NiB、NiB/Al2O3和NiBSm/Al2O3三种催化剂,它们都呈非晶结构.用等离子耦合发射光谱仪(ICP)对催化剂组分进行了分析,采用差示扫描量热法(DSC)对三种催化剂进行了热稳定性分析.结果表明,载体的引入使非晶态NiB合金的体相组成中B的含量降低.将非晶态NiB合金负载到γ-Al2O3上,可以明显改善非晶态合金的热稳定性,少量Sm可以进一步提高晶化温度.晶化激活能数据亦表明了载体和Sm对非晶结构具有良好的稳定作用.载体和Sm可能通过不同的作用提高了非晶态合金的热稳定性. 相似文献
30.
提出用两个热流变简单粘弹体的并联体系作为两相聚合物的粘弹模型,将先前的动态力学温度谱分析方法推广到两相聚合物中去.运用这种新方法从动态力学数据求出了PET/70PHB共聚物的双活化能,其中150℃左右的转变活化能为71.9kcal/mol,70℃左右的转变活化能为117.5koal/mol,这一数值与文献上PET/60PHB这个转变的活化能120kcal/mol相接近.文中还计算了共聚物在不同温度下的10s应力松弛模量,所得结果与实测值相吻合. 相似文献