Statistical theory for hydrogen bonding fluid system of AaDd type (Ⅲ): Equation of state and fluctuations

The equation of the state of the hydrogen bonding fluid system of AaDd type is studied by the principle of statistical mechanics. The influences of hydrogen bonds on the equation of state of the system are obtained based on the change in volume due to hydrogen bonds. Moreover, the number density fluctuations of both molecules and hydrogen bonds as well as their spatial correlation property are investigated. Furthermore, an equation describing relation between the number density correlation function of "molecules-hydrogen bonds" and that of molecules and hydrogen bonds is derived. As application,taking the van der Waals hydrogen bonding fluid as an example, we considered the effect of hydrogen bonds on its relevant statistical properties.     

Four-electron reduction of dinitrogen during solution disproportionation of the organodimetallic (eta-C5Me4R)2Ta2(mu-Cl)4(R = Me, Et) to a new mu-eta1,eta1-N2 complex and odd-electron organotrimetallic cluster

(C5Me5R)2Ta2Cl4 (d2-d2) disproportionates under dinitrogen to [(C5Me4R)TaCl2]2(mu-N2) and the D3h cluster cation (C5Me4R)3Ta3(mu-Cl)6+ with anionic (C5Me4R)TaCl4-.     

茂钇-铝双金属配合物催化甲基丙烯酸甲酯立规聚合

立规聚合;茂稀土催化剂;稀土;茂钇-铝双金属配合物催化甲基丙烯酸甲酯立规聚合     

纤维改性硫氧镁基仿木保温材料性能研究

为了提高硫氧镁基仿木保温材料的各项性能, 分别研究了相同长度的聚丙烯纤维(PPF)、聚乙烯醇纤维(PVAF)、玻璃纤维(GF)对其性能的影响. 结果表明: 随着纤维掺量的增加, 硫氧镁基仿木保温材料的流动性有所降低; GF对其抗压抗折强度的提高效果最明显, 其中GF掺量为1.0 kg·m^-3时早期抗压强度最高, PVAF掺量为0.5 kg·m^-3时其早期抗压强度最高; PPF明显提高了硫氧镁基仿木保温材料的耐水性, 其掺量为0.5 kg·m^-3时软化系数最大, 而GF掺量在1.0 kg·m^-3时, 浸水软化系数稍高于未加纤维的对比试件; 掺加PVAF后硫氧镁基保温材料的导热系数出现一定程度的降低, 其中PVAF掺量在1.5 kg·m^-3时其导热系数最低. GF和PPF可以明显地降低硫氧镁基仿木保温材料的收缩值, 其中GF降低自收缩效果较好, 而PPF可以明显地降低其干燥收缩值.     

烯烃聚合高性能FI催化剂的进展

FI催化剂系一近几年发展起来的烯烃聚合高性能催化剂。以它的极高的活性、聚合物分子结构的可控性、多重活性聚合等特性而引人注目。本评述首先进行该催化剂的化学描述,然后分别介绍该催化剂的主要特征、活性中心结构、聚合机理和应用,重点介绍该催化剂的五大特征。     

Free radical polymerization with catalytic chain transfer: Using NMR to probe the strength of the cobalt–carbon bond in small molecule model reactions

This work examines cobalt–carbon bond formation between the cobalt (II) macrocycle, (tetrakis(p‐methoxyphenyl)porphyrinato)cobalt (II), (TAP)Co, and a variety of radicals derived from vinyl compounds to facilitate a better understanding of the various factors affecting the cobalt–carbon bond strength in catalytic chain transfer polymerization. The reaction of (TAP)Co with the following vinylic molecules was studied: methacrylonitrile, cyclohexene, methyl methacrylate, styrene, methyl acrylate, vinyl acetate, vinyl benzoate, methyl crotonate, cis‐2‐pentenenitrile, and ethyl α‐hydroxymethacrylate. Different concentrations of each vinylic compound were added to (TAP)Co and 2,2′‐azobis(isobutyronitrile) in CDCl₃ at 60 °C. The ratio of Co(III) to Co(II) and the nature of the radical bound to the cobalt macrocycle were determined via nuclear magnetic resonance measurements. Several factors are shown to affect the reaction of the radical and the cobalt (II) species (and hence the strength of the cobalt–carbon bond in the resulting compound). These factors are as follows: the number of pathways by which a radical may be derived from the vinyl compound; the variety of radicals that can be produced from the vinylic molecule; the stability of the radical(s) generated; and the relative propagation rate of the vinyl compound. A discussion on the relevance of this study to the behavior of different monomers in catalytic chain transfer reactions is included. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6171–6189, 2006     

Statistical theory for hydrogen bonding fluid system of A_aD_d type (I): The geometrical phase transition

The influence of hydrogen bonds on the physical and chemical properties of hydrogen bonding fluid system of AaDd type is investigated from two viewpoints by the principle of statistical mechanics. In detail, we proposed two new ways that can be used to obtain the equilibrium size distribution of the hydrogen bonding clusters, and derived the analytical expression of a relationship between the hydrogen bonding free energy and hydrogen bonding degree. For the nonlinear hydrogen bonding systems, it is shown that the sol-gel phase transition can take place under proper conditions, which is further proven to be a kind of geometrical phase transition rather than a thermodynamic one. Moreover, several problems associated with the geometrical phase transition and liquid-solid phase transition in nonlinear hydrogen bonding systems are discussed.     

光场横向效应导致CO2激光器混沌运转的实验研究

对横向效应导致单纵模多横模CO_2激光器失稳进行了实验研究.观测到了经各种途径到达的激光混沌态,并对其物理机制进行了探讨.     

Af型自由基均聚反应的固化理论(Ⅲ)──高分子凝胶网络缺陷

应用高分子反应统计理论,分析了高分子网络的形成过程,讨论了A_f型自由基均聚反应凝胶网络中的缺陷悬吊环的数目及其形成几率.