Epoxidation of styrene on Si/Ti/SiO2 catalysts prepared by chemical grafting

Titania-silica (Ti/SiO2) and silica-titania-silica (Si/Ti/SiO2) catalysts were:prepared by chemical grafting using TiCl4 and tetraethyl orthosilicate (TEOS) as precursors and SiO2 as support. The prepared catalysts were characterized by UV Raman and visible Raman spectroscopies, XRD and the epoxidation of styrene; Ti/SiO2: catalyst grafted with only titanium species is not very active for epoxidation using H2O2 (30%), but is active and-selective when one uses tert-butyl hydroperoxide (TBHP). The catalyst grafted at high temperatures shows better epoxide selectivity. Si/Ti/SiO2 catalyst, the titanium-silica grafted further with TEOS, is active and selective for the epoxidation of styrene using either dilute H2O2 or TBHP, possibly due to the fact that the grafting of Ti/SiO2 with TEOS modifies the coordination structure of titanium and makes the titanium sites of Si-O-Ti-O-Si species less hydrophilic. A characteristic band at 1085cm(-1) due to Ti-O-Si species is detected for the grafted catalysts by UV resonance Raman spectroscopy. Reaction between TiCl4 and SiO2 at high temperatures favors the formation of Ti-O-Si species. Better activity and selectivity to epoxide,is found for the catalysts with more Ti-O-Si species. It is assumed that the active sites are the highly isolated Ti-O-Si species. For Si/Ti/SiO2 catalyst, the gas phase O-2 can participate in the catalytic oxidation of styrene when H2O2 is present ana:ii causes the formation of benzaldehyde. (C) 2000 Elsevier Science B.V. All rights reserved.

Capillary electrochromatography with monolithic poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase

A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically, The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.

Isospecific polymerization of styrene with modified ziegler-type catalysts

Effects of various kinds of additives as well as aging of the catalyst on the polymerization of styrene catalyzed by TiCl4/MgCl2-AlEt3 system have been studied. Experiments show that in toluene the isotacticity of polystyrene can be up to 83% for aged catalyst, whereas when the catalyst is not aged. non-stereospecific polymer is the main product. When PCl3 is used as an additive, the catalyst system gives high activity and isotacticity. The use of a mixture of AlEt3/H2O (1: 1 mole ratio) as a cocatalyst is also efficient. The catalyst [TiCl4-PCl3/MgCl2-AlEt3/H2O] displays high activity and product isotacticity (94%) with an average molecular weight up to 2 X 10(-6). When Co(acac)(3) is added to to [TiCl4/MgCl2-AlEt3] catalyst after it was aged, the isotacticity can be up to 97%. (C) 2001 Elsevier Science Ltd. All rights reserved.

Reaction-controlled phase transfer catalysis for styrene epoxidation to styrene oxide with aqueous hydrogen peroxide

The epoxidation of styrene catalyzed by a reaction-controlled phase transfer catalyst [(C18H37(30%)+C16H33(70%))N(CH3)(3))(3)](3)-[PW4O16] with H2O2 in a biphasic medium was investigated. Under certain conditions, the selectivity for styrene oxide was 95%, the conversion of styrene based on H2O2 was 85%, and the reaction time was less than 1 h. During the reaction, this catalyst powder formed soluble active species by the action of H2O2, was recovered as a precipitate, and was reused after H2O2 was used up. After two times recycling, the catalyst kept almost the same activity.

Kinetic and Size Control of Polystyrene and Polyacrylic Octadecyl Ester Lattices Via Polymerization in O/W Microemulsions

The kinetic studies of the acrylic octadecyl ester and styrene polymerization in microemulsion systems, (1) cetyl pyridine bromide (CPDB)/t-butanol/styrene/water; (2) CPDB/t-butanol/toluene + acrylic octadecyl ester (1:1, w/v)/ water; (3) cetyl pyridine bromide/styrene/formamide, were made by using dynamic laser light scattering techniques (DLS). The mechanisms of nucleation of latex particles were discussed. The most possible nucleation location of the styrene and acrylic octadecyl ester microlatex particles in aqueous microemulsion system is in aqueous phase via homogeneous nucleation. Meanwhile, parts of microlatex particles are possibly produced via swollen micelles (microemulsions) and monomer droplets nucleation. On the other hand, the most possible nucleation location of the styrene microlatex particles in nonaqueous microemulsion system is inside monomer droplets. The relationship between the amount of monomer and the size of microlatex was also investigated. It has been found that the size of microlatex particles could be controlled by changing the amount of monomer. (C) 2002 Elsevier Science B.V. All rights reserved.

Difference in Enzyme Activity and Conformation of Glucose Oxidase Before and After Purification

EEnzyme activity of commercial glucose oxidase was enhanced after purification through a strong anionic exchange resin. In order to get a better insight into this phenomenon, surface pressure–area ( –A) isotherms and surface pressure–time ( –t) isotherms was used to study the interaction and the absorption at different pH values of the subphases between octadecylamine and glucose oxidase purified by a styrene system quaternary ammonium type strongly basic anionic exchange resin. Circular dichroism (CD), electrophoresis and enzyme activity measurements were conducted to study these phenomena. A preliminary hypothesis has been suggested to explain why the enzyme activity of purified glucose oxidase was higher than that of the commercial one. © 2002 Elsevier Science B.V. All rights reserved.

苯乙烯/丙烯酸正丁酯/丙烯酸共聚微球的制备及其性能表征

通过乳液聚合法和无皂乳液聚合法制备了苯乙烯/丙烯酸正丁酯/丙烯酸共聚微球.讨论了乳化剂用量、引发剂用量、功能单体、软硬单体用量比等对微球粒径和形态的影响.利用扫描电子显微镜(SEM)、傅立叶变换红外光谱仪(FTIR)对微球的粒径、形貌和表面基团进行分析.红外光谱表明,实验室所制备的苯乙烯/丙烯酸正丁酯/丙烯酸共聚微球表面存在丰富的羧基.利用竖片生长法得到自组装的多层胶体微球薄膜.通过对薄膜的反射光谱测量,发现随着湿度的增加,峰位会产生3nm左右的红移.

一种新的芴类衍生物的三光子吸收诱导荧光和光限幅效应研究

通过对新合成的芴的一种具有对称性衍生物4-2-（7-（4-氨基苯乙烯基）-9，9-二（2-乙基己基）-9H-芴-2-）乙烯基）苯胺（BASF）的DMF溶液的研究，发现其具有很强三光子吸收频率上转换荧光发射特性，实验测出上转换荧光的波长范围是456-775nm，在510nm处的荧光强度与入射光强的三次方成正比．在0．03mol／L的浓度下就有明显的三光子吸收诱导的光限幅效应．非线性吸收系数和吸收截面分别为y=4．34×10^20 cm^3／W^2和σ3=2．4×10^-39 cm^6／W^2．

Hydrodynamics in an expanded bed of large size ion-exchange resin, and natural product adsorption

Successful applications of expanded bed adsorption (EBA) technology have been widely reported in the literature for protein purification. Little has been reported on the recovery of natural products and active components of Chinese herbal preparations using EBA technology. In this study, the hydrodynamic behavior in an expanded bed of cation resin, 001 x 7 Styrene-DVB, was investigated. Ephedrine hydrochloride (EH) was used as a model natural product to test the dynamic binding capacity (DBC) in the expanded bed. EBA of EH directly from a feedstock containing powdered herbs has also been investigated. These particles are different from commercially available expanded bed adsorbents by virtue of their large size (20S to 1030 gm). When the adsorbent bed is expanded to approximately 1.3 to 1.5 times its settled bed height, the axial liquid-phase dispersion coefficient was found to be of the order 10(-5) m(2) s(-1), which falls into the range 1.0 x 10(-6) to 1.0 X 10(-5) m(2) s(-1) observed previously in protein purification. Because of the favorable column efficiency (low axial dispersion coefficient), the recovery yield and purification factor values of EH directly from a feedstock reached 86.5% and 18, respectively. The results suggest that EBA technology holds promise for the recovery of natural products and active components of Chinese herbal preparations.

Polymerization of ionic liquid-based microemulsions: A versatile method for the synthesis of polymer electrolytes

电子邮箱fyan@suda.edu.cn

Enhanced Proton Conduction in Polymer Electrolyte Membranes as Synthesized by Polymerization of Protic Ionic Liquid-Based Microemulsions

Proton-conducting membranes were prepared by polymerization of microemulsions consisting of surfactant-stabilized protic ionic liquid (PIL) nanodomains dispersed in a polymerizable oil, a mixture of styrene and acrylonitrile. The obtained PIL-based polymer composite membranes are transparent and flexible even though the resulting vinyl polymers are immiscible with PIL cores. This type of composite membranes have quite a good thermal stability, chemical stability, tunability, and good mechanical properties. Under nonhumidifying conditions, PIL-based membranes show a conductivity up to the order of 1 x 10(-1) S/cm at 160 degrees C, due to the well-connected PIL nanochannels preserved in the membrane. This type of polymer conducting membranes have potential application in high-temperature polymer electrolyte membrane fuel cells.

Fabrication of ZnO and its enhancement of charge injection and transport in hybrid organic/inorganic light emitting devices

ZnO nanocrystals were synthesized by hydrolysis in methanol. X-ray diffraction and photoluminescence spectra confirm that good crystallized ZnO nanoparticles were formed. Utilizing those ZnO nanoparticles and poly [2- methoxy-5 - (3',7'-dimethyloctyloxy)- 1,4-phenylenevinylene] (MDMO-PPV), light emitting devices with indium tin oxide (ITO)/poly(3,4-oxyethyleneoxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS)/ ZnO:MDMO-PPV/Al and ITO/PEDOT:PSS/MDMO-PPV/Al structures were fabricated. Electrolummescence (EL) spectra reveal that EL yield of hybrid MDMO-PPV and ZnO nanocrystals devices increased greatly as compared with pristine MDMO-PPV devices. The current-voltage characteristics indicate that addition of ZnO nanocrystals can facilitate electrical injection and charge transport. The decreased energy barrier to electron injection is responsible for the increased efficiency of electron injection. (c) 2007 Elsevier B.V. All rights reserved.

新型单茂钛苯乙烯间规聚合催化剂的研究

本论文合成、表征了一系列改性单茂钦配合物，研究了这些配合物催化苯乙烯间规聚合反应行为。主要工作和结论如下：1．合成、表征了一系列双酚（胺）氧基五甲基单茂钦氯化物。在改性甲基铝氧烷（MMAO）的活化下，这些配合物可高效地催化苯乙烯间规聚合，在较高的聚合温度时（70-90℃），催化活性接近或超过五甲基氯化单茂钦的活性，在较低的铝钦比时（500／1），催化活性远远高于五甲基氯化单茂钦的活性。2．合成、表征了一系列新型单乙醇苯胺五甲基单茂钦氯化物。在MMAO的活化下，这类配合物是苯乙烯间规聚合的高效催化剂，催化活性高于母体配合物五甲基单茂钦氯化物，在较高的聚合温度和较低的铝钦比时，体现出优异的催化性能。这类配合物的催化活性随着配体的空间位阻的增大而逐渐升高。3．合成、表征了一系列新型双乙醇苯胺五甲基单茂钦氯化物。在MMAO的活化下，可以高效催化苯乙烯间规聚合，催化活性高于母体配合物五甲基单茂钦和相应的单乙醇苯胺配合物，尤其在较高的聚合温度和较低的铝钦比时，更加体现出优于母体配合物的催化性能。这类配合物的催化活性随着配体的空间位阻的增大而逐渐升高。4．合成、表征了一系列新型含曼尼希碱类配体的五甲基单茂钦氯化物。在MMAO的活化下，可高效催化苯乙烯间规聚合，催化活性远远高于母体配合物五甲基单茂钦氯化物，尤其在较高的聚合温度和较低的铝钦比时，更加体现出优于母体配合物的催化性能。这类配合物的催化活性随着配体的空间位阻的增大而逐渐升高。5．合成、表征了一种新型的多核单茂钦配合物。在MMAO的活化下，这类钦配合物可催化苯乙烯间规聚合，在优化条件下，催化活性可以达到五甲基氯化单茂钦活性的三倍，尤其在较高的聚合温度和较低的铝钦比时，更加体现出优于母体配合物的催化性能。随着中心金属原子个数的增多，催化所需的MMAO的用量逐渐减少。