负载型配位催化剂在烯烃双烯烃聚合中的应用

综述了近年来负载型配位催化剂在烯烃、双烯烃聚合中的应用研究进展，包括无机裁体有机载体、复合载体负载催化剂以及复合型主催化剂用于烯烃、双烯烃的聚合。     

含羧酸配体的鼓形有机锡氧簇合物：六聚苯基锡氧3-吲哚丁酸酯的合成及晶体结构

利用Ph3SnOH和3-吲哚丁酸以1：1摩尔比反应，合成了新型含羧酸配体的鼓形 有机锡氧簇合物：六聚苯基锡氧3-吲哚西酸酯。通过元素分析、红外光谱和X射线 单晶衍射对其结构进行了表征。测试结果表明：该化合物为三斜晶系，空间群P1， a=1.1722(6),b=1.5694（8）nm，c=1.7227(9)nm，α=116.251（8）°，β=100. 854（10）°，γ=95.606（9）°，Z=1，V=2.732(3)nm^3，Dc=1.554g·cm^-3，μ =1.420mm^-1，F(000)=1276，R=0.0630，ωR=0.0762。晶体结构中，六配位的锡原 子呈畸变的八面体构型。     

人参中总皂甙的超声波快速提取方法研究

建立了人参中总皂甙超声波半微量快速提取方法，与索氏提取法相比，此法提取时间由索氏法的1－2个工作日缩短到30min，节省大量试剂，综合提取效率提高数十倍，与索氏提取法对照分析表明，此法可完全满足人参中总皂甙的快速测定要求。     

Electroosmotic flow in a capillary annulus with high zeta potentials

The electroosmotic flow through an annulus is analyzed under the situation when the two cylindrical walls carry high zeta potentials. The analytical solutions for the electric potential profile and the electroosmotic flow field in the annulus are obtained by solving the Poisson-Boltzmann equation and the Stokes equation under an analytical scheme for the hyperbolic sine function. A mathematical expression for the average electroosmotic velocity is derived in a fashion similar to the Smoluchowski equation. Hence, a correction formula is introduced to modify the Smoluchowski equation, taking into account contributions due to the finite thickness of the electric double layer (EDL) and the geometry ratio-dependent correction. Specifically, under a circumstance when the two annular walls are oppositely charged, the flow direction can be determined from the sign of such correction formula, and there exists a zero-velocity plane inside the annulus. With the assumption of large electrokinetic diameters, the location of the zero-velocity plane can be estimated from the analytical expression for the velocity distribution. In addition, the characteristics of the electroosmotic flow through the annulus are discussed under the influences of the EDL parameters and geometric ratio of the inner radius to the outer radius of the annulus.     

2,3,7‐Triazabicyclo[3.3.0]octenes Prepared by Tandem Cascade Reaction of Allyl Azides and Olefinic Dipolarophiles

Tandem cascade reactions of allylazides and olefinic dipolarophiles to give cis‐fused 2,3,7‐triazabicyclo [3.3.0]octenes ( 5, 6 or 7 ) are reported. Therein, an intermolecular dipolar cycloaddition of azide and alkene gave a triazoline which was followed by isomerization of the triazoline to a diazoester ( 4 ) and then an intramolecular dipolar cycloaddition from the diazo functional group and the double bond in 4 to give 5 . Compound 5 may further more undergo a Michael addition to give 7‐substituted‐ 2,3,7‐ triazabicyclo [3.3.0]oct‐2‐ene ( 6 ) or a tautomerization to give 2,3,7‐triazabicyclo[3.3.0]oct‐3‐ene ( 7 ). The reaction may be manipulated to stop at a particular stage by adopting a suit able solvent or an appropriate temperature.     

The effects of polymer chain rigidification, zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite A mixed matrix membranes

The polyethersulfone (PES)-zeolite 3A, 4A and 5A mixed matrix membranes (MMMs) were fabricated with a modified solution-casting procedure at high temperatures close to the glass transition temperatures (T_g) of polymer materials. The effects of membrane preparation methodology, zeolite loading and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. SEM results show the interface between polymer and zeolite in MMMs experiencing natural cooling is better (i.e., less defective) than that in MMMs experiencing immediate quenching. The increment of glass transition temperature (T_g) of MMMs with zeolite loading confirms the polymer chain rigidification induced by zeolite. The experimental results indicate that a higher zeolite loading results in a decrease in gas permeability and an increase in gas pair selectivity. The unmodified Maxwell model fails to correctly predict the permeability decrease induced by polymer chain rigidification near the zeolite surface and the partial pore blockage of zeolites by the polymer chains. A new modified Maxwell model is therefore proposed. It takes the combined effects of chain rigidification and partial pore blockage of zeolites into calculation. The new model shows much consistent permeability and selectivity predication with experimental data. Surprisingly, an increase in zeolite pore size from 3 to 5 Å generally not only increase gas permeability, but also gas pair selectivity. The O₂/N₂ selectivity of PES-zeolite 3A and PES-zeolite 4A membranes is very similar, while the O₂/N₂ selectivity of PES-zeolite 5A membranes is much higher. This implies the blockage may narrow a part of zeolite 5A pores to approximately 4 Å, which can discriminate the gas pair of O₂ and N₂, and narrow a part of zeolites 3A and 4A pores to smaller sizes. It is concluded that the partial pore blockage of zeolites by the polymer chains has equivalent or more influence on the separation properties of mixed matrix membranes compared with that of the polymer chain rigidification.