Vinyl-polymerization of norbornene with novel anilido–imino nickel complexes/methylaluminoxane: Abnormal influence of polymerization temperature on molecular weight of polynorbornenes

Herein reported are investigations of norbornene polymerization by novel anilido–imino nickel complexes [(Ar¹NCHC₆H₄NAr²)NiBr]₂ (Ar¹ = Ar² = 2,6-dimethylphenyl, 1; Ar¹ = 2,6-dimethylphenyl, Ar² = 2,6-diisopropylphenyl, 2; Ar¹ = Ar² = 2,6-diisopropylphenyl, 3; Ar¹ = 2,6-diisopropylphenyl, Ar² = 2,6-dimethylphenyl, 4) activated with methylaluminoxane (MAO). It was found that at polymerization temperatures below 50 °C, the average molecular weights of the obtained polynorbornenes catalyzed by these four catalytic systems increase with raising temperature, displaying bimodal distribution in GPC curves. The abnormal influence of polymerization temperature could be attributed to the existence of two kinds of catalytic species: heterobimetallic species LNi(II)(μ-Me)₂AlMe₂ (I) and monometallic species LNi(II)Me (II) (L = anilido–imino ligand) at lower temperature. The former affords a lower molecular weight polymer and the latter higher molecular weight one. With raising polymerization temperature above 50 °C, the species I disappears and only species II exists in polymerization systems, resulting in a normal relation of molecular weight to polymerization temperature. From a kinetic study of the norbornene polymerization catalyzed by 1/MAO catalyst at 70 °C, the polymerization rate (R_p) can be expressed by the formulation: R_p = k[NBE]^1.93[Ni]^0.88. Moreover, the mechanism of the norbornene polymerization using the anilido–imino nickel complexes activated with MAO is also presented and discussed.     

金属铜升温熔化过程的分子动力学模拟

采用分子动力学方法模拟了金属铜的升温熔化过程.原子间作用势采用FS (Finnis-Sinclair)势，结构分析采用双体分布函数(PCF)、均方位移(MSD)等方法.计算结果表明,在连续升温过程中，金属铜在1444 K熔化，在该熔化点的扩散系数为4.31×10－9 m2•s－1.上述结论与实验值相当接近，并且比之采用EAM镶嵌原子势所作模拟得到的结果更佳，说明FS势可以用来处理象液铜这样较复杂的无序体系.本文指出了升温速率在金属熔化过程中所起的作用.     

Synthesis, crystal structure and properties of K2Ta2S10: A novel ternary tantalum polysulfide with TaS8 polyhedra forming infinite anionic chains

The new ternary alkali tantalum polysulfide K₂Ta₂S₁₀ has been synthesized by reacting TaS₂ with an in situ formed melt of K₂S₃ and S at 773 K. The compound crystallizes with four formula units in the monoclinic space group P2₁/n (No. 14) with lattice parameters of . The structure contains two different zigzag chain anions [TaS₅]⁻, running parallel to the crystallographic b-axis separated by potassium cations. The two crystallographically independent tantalum atoms are in a distorted bi-capped trigonal prismatic environment of eight sulfur atoms which was never observed before. The TaS₈ polyhedra share three S atoms on each side to form the anionic chains. The compound was characterized with FIR and Raman spectroscopy.     

The reaction of 1,2-dilithiotetrafluorobenzene with group V halides

Although the arsenic containing analogue of triptycene, 5,10-$\text{o}$-benzenoarsanthrene $\text{A}$ (E=As) was isolated some time ago [1] the related derivatives of antimony and bismuth are unknown. We now find that when 1,2-diiodotetrafluorobenzene is treated with methyllithium at -78/dg, to afford the little studied dilithiotetrafluorobenzene [2], and the appropriate metal chloride is added to the resulting solution, perfluorinated analogues of $\text{A}$ (E = As, Sb, or Bi) are obtained in good yield. These are stable volatile solids.

     

天然水源中微量铀钍含量与摄入量研究

分析了居民饮用水及其天然水源中微量铀，钍的含量，并与尿液中铀，钍含量进行了比较。结果表明，上海地区天然水源在国家规定的允许范围内，接近于尿液中铀，钍的日排出量。     

~1H MAS NMR characterization of hydrogen over silica-supported rhodium catalyst

Hydrogen species in both SiO2 and Rh/SiO2 catalysts pretreated in different atmospheres (H2, O2, helium or air) at different temperatures (773 or 973 K) were investigated by means of 1H MAS NMR. In SiO2 and O2-pretreated catalysts, a series of downfield signals at -7.0, 3.8-4.0, 2.0 and 1.5-1.0 were detected. The first two signals can be attributed to strongly adsorbed and physisorbed water and the others to terminal silanol (SiOH) and SiOH under the screening of oxygen vacancies in SiO2 lattice, respectively. Besides the above signals, both upfield signal at -110 and downfield signals at 3.0 and 0.0 were also detected in H2-pretreated catalyst, respectively. The upfield signal at -110 originated from the dissociative adsorption of H2 over rhodium and was found to consist of both the contributions of reversible and irreversible hydrogen. There also probably existed another dissociatively adsorbed hydrogen over rhodium, which was known to be p hydrogen and in a unique form of "delocalized hydrogen". It wa     

聚合物电流变体

本文概述了电流变体的发展概况，电流变机理、电流变效应的影响因素及聚合物电流变体的研究现状，并介绍了电流变化的组成春在机械制造、自动控制等领域的应用前景。     

Application of Iodide Ion Selective Electrode to the Study of Stepwise Formation Constant and Solubility Product of Lead Iodide

Iodide ion-selective electrode were studied, prepared and applied for the complex formations and solubility product determination. The thermodynamic formation constant of PbI⁺ and the solubility product of PbI₃ were found to be 54 and 9.2 × 10^?9, respectively. The formation constant of PbNO₃⁺ was calculated to be 4.6 from the different formation constant of PbI⁺ in perchlorate and nitrate media.     

Carbon anode materials from polysiloxanes for lithium ion batteries

Three kinds of silicon-containing disordered carbons have been prepared by pyrolysis of polysiloxanes with different amounts of phenyl side groups. X-ray powder diffraction, X-ray photoelectron spectroscopy and electrochemical capacity measurements were performed to study their behaviors. Graphite crystallites, micropores, and silicon species affect their electrochemical performances. All of them present high reversible capacities, >372 mAh/g. Since the graphite crystallites are very small, they contribute very little to reversible capacity. The number of micropores produced by gas emission during the heat-treatment process decides whether they exhibit reversible capacity. Si mainly exists in the form C–Si–O and influences the irreversible capacity. There is no evident capacity fading in the first ten cycles, indicating promising properties for these disordered carbons.