SYNTHESES OF POLYMERIC LIGAND-BOUND RHODIUM COMPLEXES AND THEIR CATALYTIC APPLICATION FOR THE HYDROFORMYLATION OF DIISOBUTYLENE

Ten polymeric ligand bound rhodium complexes were synthesized by the reaction ofRh_2(CO)_4Cl_2 and functional cross-linked poly-styrene consisting of amine, aminophosphine andphosphite groups. These polymeric catalysts were used for hydroformylation of diisobuty-lene at a temperature of 110℃, under pressures of 100, 80, 60 kg/cm~2 and H_2/CO = 1: 1 for 6h, benzene being used as the solvent. Most of the catalysts prepared showed good catalyticproperties. IR spectral analysis indicates that the polymeric amine bound rhodium catalystspossess a polydentatc structure. The rhodium elution of the catalysts was examined. Therelationship between the structure of ligands, the rhodium elution and catalytic activity wasdiscussed. A curve of rhodium elution v.s. the number of catalytic application cycles wasinvestigated. The influence of reaction conditions and additives on the loss of rhodium wasalso studied. The possible mechanism of rhodium elution of the polymeric catalysts wassuggested.     

Al2O3负载Cu,Fe或Ni掺杂氧化钼催化乙苯氧化脱氢（英文）

Molybdenum-based catalysts supported on Al2O3 doped with Ni, Cu, or Fe oxide were synthesized and used in ethylbenzene dehydrogenation to produce styrene. The molybdenum oxide was sup-ported using an unconventional route that combined the polymeric precursor method (Pechini) and wet impregnation on commercial alumina. The samples were characterized by X-ray diffraction (XRD), N2 adsorption-desorption isotherms, temperature-programmed reduction of H2 (H2-TPR), and thermogravimetric (TG) analysis. XRD results showed that the added metals were well dis-persed on the alumina support. The addition of the metal oxide (Ni, Cu, or Fe) of 2 wt% by wet im-pregnation did not affect the texture of the support. TPR results indicated a synergistic effect be-tween the dopant and molybdenum oxide. The catalytic tests showed ethylbenzene conversion of 28%–53% and styrene selectivity of 94%–97%, indicating that the addition of the dopant improved the catalytic performance, which was related to the redox mechanism. Molybdenum oxides play a fundamental role in the oxidative dehydrogenation of ethylbenzene to styrene by its redox and acid–base properties. The sample containing Cu showed an atypical result with increasing conver-sion during the reaction, which was due to metal reduction. The Ni-containing solid exhibited the highest amount of carbon deposited, shown by TG analysis after the catalytic test, which explained its lower catalytic stability and selectivity.     

SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅰ)

Copolymer of styrene-divinylbenzene in bead form (with DVB 8%, average pore radius 3.0×10~2, specific surface area 25m~2/g, particle size 0.2—0.4mm) was made by the suspension polymerization. After chloromethylation, the beads were then reacted with lithium diphenyl phosphine and various amines separately. Two types of polymeric ligands, i.e. polyvinylbenzyl diphenyl phosphine and eight kinds of polyvinylbenzyl amines were thus obtained. In order to prepare the polymer-bound rhodium complexes, the ligands were then reacted with [Rh(CO)_2CI]_2. The initial composition and structure of the polymeric complexes were verified by IR spectra. The complexes synthesized above were used to catalyze the hydroformylation of diisobutylene under conditions of 110℃, 100(120) kg/cm~2 and H_2/CO=1:1. The effects of the donor atoms (N, P) on the activity of the two types of catalysts and the N-substituted groups on the activity 'of polymeric amine-rhodium complexes were examined.     

Synthesis Structure and Behavbr of Polymeric Drugs Covalently Linked 5-Fluorouracil

Four series of polymeric drugs with 5-Fluorouracil(5-FU) cova-lently linked in side chain were synthesized by the use of starch and carboxylmethylcellulose and two new 5-FU derivatives were also synthesized by using molecular sieve as a catalyst.Their structures were determined by IR,1H NMR and mass spectra.The changes in the Nitrogen content of polymeric drugs with reaction conditions and the influences of the N content on their limiting viscosity were studied.The hydrolysis of 5-FU from starch and carboxylmethylcellulose derivatives in various of buffer were researched by simulating physiologically acid-alkali enviroment.In addition,anticancer activity(in vivo and in vitro) of some starch derivative has been preliminaryly observed.     

烷基聚葡糖苷C9.6G1.3/n-C4H9OH/n-C6H14/H2O微乳液体系的介电弛豫谱研究

The pseudotertiary phase diagram of the microemulsion system alkyl polyglucoside/n-butanol/n-hexane/water was plotted at （30.0±0.1） ℃. The dielectric measurements, including permittivity, conductivity, relaxation strength, characteristic relaxation time, etc,, were applied to investigate the microstructure of the system. Unique dielectric relaxations were observed over the frequency range of 5-10^7 Hz, taking place possibly through an interracial polarization mechanism. According to the results obtained from dielectric spectroscopy, the structures of the microemulsion O/W, BC and W/O were determined, and some dielectric and phase parameters were calculated.     

溶胶-凝胶法制备Ca10(PO4)6(OH)2 /TiO2复合涂层及其在模拟生理体液中的行为

The composite films consisting of hydroxyapatite (HAP) submicron particles embedded in the gel composed of the titania nanoparticles were prepared on commercial Ti6A14V plates with titania buffer layer obtained by a spin-coating technique. The films were calcined in air at various temperatures, and the bioactivities of the films were investigated by immersing them in acellular simulated body fliud (SBF). X-ray diffraction(XRD), Fourier transform infrared spectroscopy (FTIR), Field emission-scanning electron microscopy(FESEM) and Energy dispersive X-ray (EDS) analysis were employed to investigate the phase formation and structure of the films before and after immersion, and the variations of Ca and P contents in SBF were measured by Inductively Coupled Plasma Spectroscopy(ICP). The results show that the as-prepared films were dense, homogeneous, all well-crystallized, and there was a close interracial bond between the film and the substrate. The characterisatics of the grown layer on the surfaces of the HAP/TiO2 films after immersion in SBF for different periods of time are specially discussed.     

H2在非晶态合金Ni40Fe40P20表面的吸附行为

With the level of B3LYP/Lanl2dz of density functional theory and advisable adsorption models designed, the adsorption properties of the most stable cluster of Ni₂Fe₂P were calculated, and four stable configurations with the adsorption of hydrogen were gained. The geometries and HOMO contributions of 3d orbital of metal atoms and energy level properties of adsorption configurations were concerned and their Infrared Spectrum were simulated and predicted. The bond lengths and bond orders and vibration frequencies concerned synthetically, the adsorption mechanisms of hydrogen molecular on amorphous alloys Ni₄₀Fe₄₀P₂₀ surfaces were discussed in the microcosmic aspect. The hydrogen molecules adsorbing on the clusters were dissociated. In the clusters′ Infrared Spectrums of hydrogen adsorption, there were the vibration peaks with the frequency less than 500 cm^-1 caused by metal atoms and other vibration peaks with the frequency more than 500 cm^-1 caused by hydrogen atoms. Compared with the energy level DOS of the clusters before and after adsorption, it was found, that the new adsorption activity sites generated after the adsorption of hydrogen, as well as easy way for metal atoms providing electrons and participating subsequence reactions were gained.     

青霉素G钾盐对SDS水溶液物理化学性质的影响及其在SDS/n-C5H11OH/H2O体系中的释放

The effects of penicillin potassium salt （PenK） on the solubility, Krafft temperature TK, critical micelle concentration CMC of SDS micelle and the phase behavior of SDS/n-C5H11OH/H2O system were studied. The partial phase diagrams of SDS/PenK/H2O system at different temperatures were determined. The release amounts of PenK in SDS/n-C5H11OH/H2O system and the distribution coefficient of PenK between micelle and water were measured by UV-Vis spectroscopy. The results show that in the presence of PenK, the CMC of SDS was decreased while the TK of SDS was increased and the solubility of SDS in both water and SDS/n-C5H11OH/H2O oil in water （O/W） microemulsion was decreased, but increased in water in oil （W/O） microemulsion. SDS micelles and SDS/n- C5H11OH/H20 O/W microemulsion could accelerate the release rate of PenK. The addition of SDS and water could both increase the release rate of PenK, whereas the presence of n-C5H11OH reduced the release rate of PenK. The above results were related to the electrostatic repulsion between PenK and SDS.     

SYNTHESIS OF POLYMER—SUPPORTED PALLADIUM CATALYSTS AND THEIR CATALYTIC BEHAVIOR FOR THE SELECTIVE HYDROGENATION OF MESITYL OXIDE

Copolymer of styrene-divinylbenzene in bead from was made by suspension polymerization.After chloromethylation and amination,five kinds of polymeric amines were thus obtained.These polymers were reacted with palladium chloride,and were then reduced.The polymer-supported catalysts synthesized above were used to catalyze the selective hydrogenation of mesityl oxide under reaction conditions of 80℃ and 10kg/cm^2,using methanol as a solvent.The catalytic activity and MIBK(methyl isobutyl ketone) formation selectivity of the catalysts were examined.     

微乳液合成胶体CuO/γ-Al2O3及其催化芳香硝基化合物还原（英文）

Monodispersed colloidal copper oxide nanoparticles were synthesized by water-in-oil microemulsion using CuCl 2·H2O and NaOH.The effect on CuO particle size was studied by varying the water-to-surfactant molar ratio,precursor concentration and molar ratio of NaOH to CuCl2.The morphology,size and size distribution of the particles were studied by transmission electron microscopy and dynamic light scattering.Dispersion destabilization of the colloidal copper oxide nanoparticles was detected by a Turbiscan apparatus.CuO/γ-Al2O3 catalysts were prepared by dispersing highly stable CuO nanoparticles on γ-alumina by mechanical stirring.The catalysts were analyzed by scanning electron microscopy,transmission electron microscopy,X-ray photoelectron,and X-ray diffraction,which confirmed the uniform dispersion of CuO on the support.The reduction of the nitro aromatic compounds,4-nitrophenol,3-nitrophenol,and 2-nitrophenol,were studied.The CuO/γ-Al2O3 catalysts were active for the reduction of these nitro aromatic compounds.     

STUDIES ON THE POLYMERIZATION OF β-CYCLODEXTRIN WITH EPICHLOROHYDRIN*

Different proportions of β-cydodextrin and epichlorohydrin were used to prepare a group of β-cyclodextrin polymers. The relationship between the reaction extent and the molar ratios of reactants was discussed according to the results of ~1H-NMR, ~(13) C-NMR spectra and elemental analysis. Especially, high resolution ~1H-NMR spectra were usd for studying the reaction active sites and the extent of reaction. The solubility of oil soluble drugs in water was largely improved in the presence of water-soluble β-cyclodextrin polymer.     

La2Mo2O9在低氧分压条件下的电导率及热膨胀测试

The electrical conductivity and thermal expansion of La2Mo2O9 under low oxygen partial pressure were studied with the help of thermoelectric power and dilatometric measurements, respectively. The ionic conduction of La2Mo2O9 was predominant with the electronic transference number less than 0.05 above an oxygen partial pressure of about Po2=10^-7 Pa at 700℃, and below this pressure the electronic conduction became obvious. The defect reaction and small polaron hopping among molybdenum sites were proposed to explain the electronic conduction. Accompanying the phase transition, there was a sharp increase of thermal expansion, which became more serious under low oxygen partial pressure. The substitution of lanthanum by neodymium led to the increase of electrical conductivity but the decrease of phase stability.     

Kinetic study of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst

The kinetics of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst were studied.Performance test runs were carried out in a fixed-bed integral reactor.Using a power-law rate expression for the surface reaction kinetics and independent law for deactivation kinetics,the experimental data were analyzed both by integral and a novel differential method of analysis and the results were compared.To avoid fluctuation of time-derivatives of conversion required for differential analysis,the conversion-time data were first fitted with appropriate functions.While the time-zero and rate constant of reaction were largely insensitive to the function employed,the rate constant of deactivation was much more sensitive to the function form.The advantage of the proposed differential method,however,is that the integration of the rate expression is not necessary which otherwise could be complicated or impossible.It was also found that the reaction is not limited by external and internal mass transfer limitations,implying that the employed kinetics could be considered as intrinsic ones.     

Surface Microstructure and Component Changes of Chromium-resistant Enterobacter Cloacae CYS-25 Strain

Enterobacter cloacae CYS-25 strain was isolated from a chromate plant. This bacterium was capable of resisting high hexavalent chromium concentration and reducing Cr（VI） under aerobic condition. CrO4^2- stimulated the increase of bacterial size and production of compact convex paths containing chromium on the bacterial surface. The increase of bacterial size was caused by integrative growth but not extracellular polymeric substance hyperplasia. IR and SDS-PAGE analyses showed the extracellular polymeric substance （EPS） components were mainly proteins and had no obvious changes whether the strains were induced by Cr（VI） or not. The EPS was amorphous and contained trivalent chromium. Under CrO4^2- growth condition, the extracellular substance of Enterobacter cloacae CYS-25 strains and Cr（VI） had redox reaction. The products were Cr^3＊-protein complexes which formed a piece of compact convex paths on the surface of bacteria and prevented Cr（VI） from entering into cells.     

SYNTHESIS AND CHARACTERIZATION OF POLYSILOXANE CONTAINING OLIGO(OXYETHYLENE)SULFATE SALT

Solvent-free polymeric alkali-metal ion conductors, consisting of a comb-like polysiloxane with oligo(oxy-ethylene) side chains and pendant sulfate groups were synthesized by the hydrosilylation of allyl oligo(oxyethylene) sulfatesalt and allyl methoxy oligo(oxyethylene) with poly(methylhydrosiloxane). The factors influncing the ionic conductivity ofthe resulting polymer such as the electrolyte content and the nature of the alkali-metal were investigated. The temperaturedependence of conductivity was determined, and the ionic conductivity of the polymer follows the Vogel-Tammann-Fulcher(VTF) equation.     

Partial oxidation of methane in Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3-δ ceramic membrane reactor

Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3δ(BSCFNiO) perovskite oxides were synthesized using a combined EDTA-citrate complexation method,and then pressed into disk and applied in a membrane reactor.The performance of the BSCFNiO membrane reactor was studied for partial oxidation of methane over Ni/α-Al 2 O 3 catalyst.The time dependence of oxygen permeation rate and catalytic performance of BSCFNiO membrane during the catalyst initiation stage were investigated at 850 C.In unsteady state,oxygen permeation rate,methane conversion and CO selectivity were closely related to the state of the catalyst.After 300 min from the initial time,the reaction condition reached to steady state and oxygen permeation rate were obtained about 11.7cm 3 cm 2 min 1.Also,the performance of membrane reactor was studied at the temperatures between 750 and 950 C.The results demonstrated good performance for the membrane reactor,as CH 4 conversion and CO selectivity permeation rate reached 98% and 97.5%,respectively,and oxygen permeation rate was about 14.5 cm 3 cm 2 min 1 which was 6.8 times higher than that of air-helium gradient.Characterization of membrane surface by SEM after reaction showed that the original grains disappeared on both surfaces exposed to the air and reaction side,but XRD profile of the polished surface membrane indicated that the membrane bulk preserved the perovskite structure.     

Synthesis of a novel water-soluble polymeric UV-absorber for cotton

A water-soluble polymeric UV-absorber with polyvinylamine as backbone and benzotriazole type UV absorber as anti-UV functional group was synthesized by grafting brominated(2’-acetoxy-5’-methylphenyl)-2H-benzotriazole onto polyvinylamine. The intermediates and synthesized polymeric UV absorber were characterized by ~1H NMR,MS,IR and UV spectroscopy.The finishing properties of the polymeric UV absorber on cotton were investigated to show good UV protection property and wash fastness.     

共沉淀法制备负热膨胀性ZrW2O8粉体及其粒径控制初探

Negative thermal expansion (NTE) material ZrW₂O₈ powders were synthesized using co-precipitation route. The precursor of ZrW₂O₈ was studied by Thermogravimetric and differential scanning calorimetry (TG-DSC). The structure and morphology of the resulting powders were characterized by Powder X-ray diffraction (XRD) and Scanning electron microscopy (SEM), respectively. The results showed that the samples were single phase of α-ZrW₂O₈ with regular shape. High temperature X-ray diffraction measurement indicated that the thermal expansion coefficient of ZrW₂O₈ was -10.35 × 10^-6 K^-1 in the temperature range from room temperature to 150 ℃, -3.08 ×10^-6 K^-1 from 200 ℃ to 600 ℃ and the average value was -5.38 × 10^-6 K^-1. At the same time, polyethylene glycol (PEG) was used as dispersant to primary control the size of ZrW₂O₈.     

电镀烧结法制备Ti/SnO2-Sb2O4电极的研究

The Ti/SnO₂-Sb₂O₄ electrode has been prepared by the electroplate-sinter method. The effect of SbCl₃ adding amount and sintering temperature on its electrode lifetime and oxygen evolution potential were investigated by means of EDX, SEM and XRD analysis. The results indicated that the electrode appeared the best performance when the SbCl₃ adding amounts was 0.2g and the sintering temperature was 550℃. In optimized conditions Ti substrate was entirely covered by SnO₂-Sb₂O₄ and the combinations among them were tight. Due to the use of electroplate method, the electrical conductivity, the oxygen evolution potential and the electrode lifetime were increased, so the elec-tro-catalytic activity and the electrochemical stability of the prepared electrode were found to be superior.     

聚肽接枝共聚物的自组装行为研究

Polymeric micelles of poly(γ-benzyl L-glutamate)(PBLG)-poly(ethylene oxide)(PEO) graft copolymer were prepared by the dialysis method in deionized water. Fluorescence spectroscopy, nuclear magnetic resonance(NMR) and transmission electron microscope(TEM) were used for the investigation of the self-assembly of PBLG-PEO graft copolymer. Fluorescence spectrosco0y measurements suggest that PBLG-PEO graft copolymer associates to form polymeric micelles in water. ^1H NMR measurements further prove that in aqueous medium PBLG-PEO graft copolymer could assemble into polymeric micelles with PBLG segments as the hydrophobic inner core and PEO segments as the hydrophilic shell. The results of the TEM observations show that the polymeric micelles of PBLG-PEO graft copolymer are almost spindly shaped, which are different from the morphology of the spherical micelles formed by PBLG-PEO block copolymer. Polymeric micelles formed by polypeptide copolymer have potential application as drug carrier in controlled-release delivery system.