COORDINATION COPOLYMERIZATION OF STYRENE WITH MALEIC ANHYDRIDE BY RARE-EARTH COORDINATION CATALYSTS

The study on coordination copolymerization of styrene (S) with maleic anhydride (MA) by rare-earth coordination catalysts, NdL_3-Al(i-Bu)_3, has been successfully carried out for the first time. Some features, kinetic behavior, and mechanism of the SMA copolymerization by Nd(naph)_3-Al(i-Bu)_3 system are described and discussed. The copolymex of styrenemaleic anhydride prepared by the NdL_3-Al(i-Bu)_3 systems in benzene at 50℃ is an alternating-rich white powder having high number-average molecular weight of 6—8.5×10~5. The overall activation energy for the polymerization was found to be 10.5KJ/mol. The polymerization was not suppressed by addition of hydroquinone. The catalytic activity of various ligands in NdL_3 for the copolymerization decreases in the following order: Nd (naph)_3>Nd-(P_(507))_3～NdCl_3-6H_2O>Nd(P_(204))_3>Nd(acac)_3. 3H_2O. The experimental results are explained based on a mechanism to be the coordination-type copolymerization in terms of the participation of a monomer-monomer c     

铬（Ⅲ）邻菲咯啉,8—羟基喹啉配合物／Y型分子筛的制备及苯酚催化羟化

制备了铬（Ⅲ）邻菲咯啉，８－羟基喹啉配合物／Ｙ型分子筛，利用元素分析，ＳＥＭ，ＵＶ－ＶｉｓＢＥＴ及ＸＲＤ等方法确定了分子筛选笼中金属配合物的生在及其晶体结构，考察了实验参数对苯酚转化率及产物选择性的影响。     

杂多酸的固载化─关于制备负载型酸催化剂的一般原理

杂多酸同时具有酸和氧化－还原的催化特性，有着很广泛的应用前景．这类化合物在一系列精细合成中取代硫酸作为催化剂以满足环保的要求，显示出了很大的潜力．杂多酸固载化后，不仅能在液相氧化和酸催化反应中把催化剂从反应介质中很方便地分离出来，而且还为这类均相催化反应的多相化，甚至利用催化蒸馏新工艺等创造了应有的条件，可以使生产工艺大大简化，获得更广泛的应用．本文以很好表征过的多种孔性材料，包括氧化物，如Ａｌ_２Ｏ_３、ＳｉＯ_２、ＴｉＯ_２、硅藻土、膨润土和来源不同的活性炭为载体，考察了负载杂多酸催化剂的催化活性．在大量前期工作的基础上，通过总结载体对固载杂多酸催化活性的影响等，探讨载体的内在性质在杂多酸固载、吸附和催化反应中的作用本质，为由吸附法制备各种负载型固体酸催化剂在液相中的应用提供可资参考的模型．     

Quantum chemistry investigation on the active site of Mn-SOD

In this paper, we carried out a theoretical study on the active site structures of the Mn-SOD with ab initio Hartree–Fock SCF method, and analyzed the molecular orbital energies, charges and atomic orbital contribution to the frontier molecular orbital.     

盐卤硼酸盐化学(非汉字字符)——MgO·nB_2O_3-18%MgCl_2-H_2O过饱和溶液20℃结晶动力学

用结晶动力学方法对不同摩尔比的 Mg O/B2 O3在摩尔分数为 1 8% Mg Cl2 -H2 O中的过饱和溶液在2 0℃的结晶动力学过程进行了研究 .n(Mg O) /n(B2 O3) =1 /1和 1 /1 .5时分别结晶析出 2 Mg O· 2 B2 O3·Mg Cl2 · 1 4H2 O和 2 Mg O· 3 B2 O3· 1 5 H2 O(多水硼镁石 ) .n(Mg O) /n(B2 O3) =1 /2时依次结晶析出 Mg O·3 B2 O3· 7.5 H2 O,Mg O· 2 B2 O3· 9H2 O和 2 Mg O· 3 B2 O3· 1 5 H2 O(多水硼镁石 ) 3种固相 .n(Mg O) /n(B2 O3)=1 /3时结晶析出不同结晶水的六硼酸镁 Mg O· 3 B2 O3· 7H2 O和 Mg O· 3 B2 O3· 7.5 H2 O.析出固相采用X射线粉末衍射、红外光谱和热分析进行物相鉴定 .拟合并给出结晶动力学方程 ,同时对水合镁硼酸盐的结晶反应机理进行了探讨     

Application of diaza-18-crown-6-capped beta-cyclodextrin bonded silica particles as chiral stationary phases for ultrahigh pressure capillary liquid chromatography

Two bonded chiral stationary phases (CSPs), 8-aminoquinoline-2-ylmethyl- and 8-aminoquinoline-7-ylmethyl-diaza-18-crown-6-capped [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl silica particles (non-porous, 1.5 microm), have been prepared and evaluated using capillary liquid chromatography at high pressures (> or = 8000 p.s.i.). High column efficiency (up to 400 000 plates m(-1)) was achieved for chiral separations. These CSPs with two recognition sites, i.e. substituted-diaza-18-crown-6 and beta-cyclodextrin combined with high chromatographic efficiency provide good resolution of a variety of enantiomers and positional isomers in relatively short times under reversed-phase conditions. After inclusion of a Ni (II) ion from the mobile phase, the positively charged crown ether-capped beta-cyclodextrin facilitates specific static, dipolar, and host-guest complexation interactions with solutes.     

反胶束笼对纳米氯化银反应性能的微环境限定

研究了反映束中直径为１０￣１７ｎｍ的ＡｇＣｌ微料与亚甲基蓝之间的作用，比较了阴离子型和非离子型表面活性剂组成的反胶束微环境的影响，讨论了亚甲基蓝在粒子上的吸附，二聚体形成的钠米ＡｇＣｌ粒子对亚甲基蓝荧光猝灭机制。     

硅胶键联MPc的制备及其在氧活化中的作用

过渡金属酞等配合物（MPC）用手均相液相氧化中作催化剂已有不少报导，象许多均相催化剂一样，MPC用于均相反应存在着难于从反应体系中分离出来的问题．把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法．我们曾尝试把MP。固载在分子筛载体和硅胶载体上，并用ESR研究其对O2的活化作用[1，2]．本文报导MPc通过共价键键联固载在SiO2上，并研究其对O2的活化作用．1实验部分1．1试剂HSIC13为日本东京化成株式会社产品，二级试剂·发烟硫酸（SO。质量分数大于20％）为分析纯试剂．PCl5为化学纯试…