Synthesis of novel chitosan resin derivatized with serine diacetic acid moiety and its application to on-line collection/concentration of trace elements and their determination using inductively coupled plasma-atomic emission spectrometry

A novel chelating resin functionalized with serine diacetic acid moiety was synthesized by using chitosan as base material, and applied to the collection/concentration of trace elements in environmental water samples, followed by the determination using inductively coupled plasma-atomic emission spectrometer (ICP-AES). The synthesized resin, crosslinked chitosan serine diacetic acid (CCTS-SDA), showed good adsorption behavior toward trace amounts of Cd, Pb, Cu, Ni, V, Ga, Sc, In, and Th in a wide pH range. Additionally, rare earth elements also can be retained on the resin at neutral pH region. The adsorbed elements can be easily eluted with 1 mol L⁻¹ of nitric acid, and their recoveries were found to be 90-100%. The CCTS-SDA was packed in a mini-column, which was then installed in a computer-controlled auto-pretreatment system (Auto-Pret System) for on-line trace elements collection and determination with ICP-AES. Experimental parameters which related to the improvement of sensitivity and reproducibility were optimized. The limits of detection (LOD) for 13 elements were found to be in sub-ppb level. The proposed method with CCTS-SDA resin was successfully applied to the determination of trace elements in river water samples. The method was validated by determining a certified reference material of river water, SLRS-4.     

High compact melamine-formaldehyde microPCMs containing n-octadecane fabricated by a two-step coacervation method

Microcapsules containing n-octadecane were successfully fabricated by an in-situ polymerization process with melamine-formaldehyde (MF) prepolymer and a hydrolyzed copolymer of styrene and maleic anhydride (SMA) as shell materials. To achieve a long service time of microcapsules containing phase change materials (microPCMs), the compactness of shells was improved by adding the MF prepolymer twice. The mechanism of this method was a two-step coacervation (TSC) under the help of hydrolyzed SMA compared to a one-step coacervation (OSC). To understand the influence of both coacervations, properties of shells were investigated in terms of morphologies, density, thickness, and stability by means of scanning electron microscopy (SEM), transmission electron microscopy, and thermal gravimetric analysis (TGA). The data of shells thickness were achieved from the cross-section SEM images. It shows that the average thickness of shells from two kinds of process are 0.1 μm. The density and stability in water of shells fabricated by TSC are both higher than that of shells by OSC. TGA curves show the expected microPCMs of TSC losing weight from 200 to 400 °C. The release curves, relationship between time and logarithmic residual weight of core, show there are two decrease-linear steps after curve regression. It can be concluded from all these results that the TSC method may be a promising method leading to a compact shell structure for various application.     

含羞草中总黄酮的提取与分离纯化

确定含羞草中总黄酮的最佳提取部位,并对其初步分离纯化。通过正交试验,分别筛选含羞草根部、茎叶及种子中总黄酮的最优提取条件,比较三者黄酮总含量,最终确定提取部位为茎叶,最佳提取条件:以70%乙醇为溶剂,按照1∶8配料比,在55~58℃下超声50 min。提取液依次用石油醚、乙酸乙酯液液萃取,蒸干上样,用乙醇水溶液以4 m L/min梯度洗脱Diaion HP–20大孔树脂,收集洗脱液并用液相色谱监测每个梯度洗脱液的总黄酮含量,得到分离纯化过的黄酮类物质。当40%乙醇洗脱部位总黄酮含量最高,达57.7%。该工艺确定了含羞草中茎叶部位总黄酮含量最高,大孔树脂初步纯化黄酮类物质有效,为含羞草中黄酮类物质的应用提供了依据。     

High impact resistance epoxy resins by incorporation of quadruply hydrogen bonded supramolecular polymers

A bisphenol A based epoxy was incorporated with a quadruply hydrogen bonded supramolecular polymer as a toughening agent to prepare a composite epoxy resin with higher impact resistance. The supramolecular polymer comprising poly-(propylene glycol) bis(2-aminopropyl) ether chains and 2-ureido-4[1H]-pyrimidinone moieties (UPy) self-assembled into spherical domains with sizes of 300 nm to 600 nm in diameter by micro phase separation in bulk epoxy matrixes. A significant improvement of 300% in impact resistance of the supramolecular polymer incorporated epoxy resin was obtained when the content of supramolecular polymer was 10 wt%. Tensile tests showed that the mechanical properties of the modified epoxy resin containing the hydrogen-bonded supramolecular polymers are also improved compared with those of the neat epoxy resin.     

Preparation and properties of waterborne epoxy resin modified by poly(meth)acrylates containing long fluorinated side chains

Abstract

Two waterborne poly(meth)acrylates containing fluorinated side chains (PALF and PASF) were synthesized by conventional radical copolymerization. Then waterborne epoxy composites with hydrophobic surface were obtained through a phase-inversion emulsion technique, using the PALF and PASF acrylates as reactive surface additives. Contact angle measurements and X-ray photoelectron spectroscope were employed to characterize the surface properties and the results confirmed that the fluorine atoms in the longer fluorinated side chains migrated to the outmost layer more efficiently. The effect of the fluorinated content and the length of the fluorine side chain on thermal and bulk properties of the waterborne epoxy resin was investigated. With increasing the fluorinated content or the length of the fluorine side chain, the contact angles and thermal properties improved while the mechanical properties showed no deterioration.     

咪唑封端聚氨酯予聚体改性环氧树脂E-51/双氰双胺固化体系性能研究

以聚丙二醇PPG10 0 0、甲苯二异氰酸酯 (TDI)、咪唑为原料 ,合成了咪唑封端的聚氨酯予聚体 ,简称扩链脲TIEU .利用DSC、粘弹谱仪、冲击试验机及扫描电镜 (SEM)等手段对TIEU改性的环氧树脂E 5 1/双氰双胺(dicy)固化体系的反应活性、动态力学行为、冲击性能、断裂面形态结构进行了系统研究 .实验结果表明 ,改性后的E 5 1 dicy体系反应活性明显提高 ,固化反应的表观活化能由未改性体系的 131kJ mol降至 75～ 80kJ mol.与咪唑促进体系比较结果显示 ,两种固化反应的促进机制具有一定的差异 .另外与未改性体系相比 ,经过改性的环氧树脂体系冲击强度提高 2～ 3倍 ,而玻璃化温度和模量基本不变 ,冲击断面呈韧性断裂     

二乙烯基苯为交联剂COPNA树脂的研究

以煤沥青为单体、二乙烯基苯（DVB）为交联剂,在对甲苯磺酸的催化作用下合成了缩合多环芳烃（COPNA）树脂。研究了工艺条件对COPNA树脂的收率、溶解性能、软化点和焦化率的影响;此外,采用扫描电镜（SEM）和微分扫描量热法（DSC）研究了COPNA树脂的形成及相转变行为。结果表明：煤沥青含有“惰性”组分,导致COPNA树脂的收率偏低,其收率偏低,其收率最高为42.6%;与煤沥青比较,COPNA树脂的溶解性能较差;COPNA树脂具有良好的工艺性和耐热性;COPNA树指的形成是以球晶方式来进行的,因此不同反应时间树脂的相转变行为有很大的差异。     

Na_3Eu(DPA)_3-PC树脂的制备及其发光性能

根据稀土有机配合物 Na3Eu(DPA) 3(DPA:2 ,6-pyridine dicarboxylic acid)的发光强和热稳定性高的特点 ,采用加热方法将 Na3Eu(DPA) 3掺入 PC树脂中 ,制成发光塑料树脂 .其发光性能结果表明 ,Na3Eu(DPA) 3掺入 PC树脂后 ,仍保持稀土有机配合物原有的发光特性 ,制成的 Na3Eu(DPA) 3-PC树脂复合材料具有良好的发光性能 ,其发光强度与稀土有机配合物 Na3Eu(DPA) 3掺入的比例量有关 ,但没有一定的线性关系 .     

Polymer‐supported reagents,catalysts, and sorbents: Evolution and exploitation—A personalized view

The solid‐phase method for oligopeptide synthesis was introduced by Professor Bruce Merrifield in 1963, but in practice the origins of polymer‐supported reagents, catalysts, and so forth trace back to the early development of ion exchange and catalysis by sulfonic acid resins. This highlight summarizes how the evolution of solid‐phase organic synthesis occurred in parallel with the development of supported reactive species and indicates the interchange between these areas in the last 30 years or so. The treatment is essentially a personalized one as seen from the author's own laboratory in the United Kingdom and is not intended to review the whole field. The emergence of the international series of conferences on polymer‐supported organic chemistry is emphasized as a key development that stimulated and maintained the area before its importance was recognized more widely by both academic and industrial chemists. The requirement of robotic technologies, as the basis for high‐throughput combinatorial and parallel synthesis in the pharmaceutical industry, has brought the relevance of supported chemistry to the attention of all synthetic chemists. At the same time, the recognition that all industrial chemical processes need to meet appropriate environmental standards has focused attention on the use of heterogenized reactive species as a potentially important technology for achieving the greening of chemistry. These two factors have brought polymer‐supported reactive chemistry to center stage, so to speak, and the early principles laid down over 2 decades ago are now being developed and exploited at an amazing rate. From a rather slow start, through a number of ups and downs in its development, the area of polymer‐supported chemistry now seems poised to join the more routine world of synthesis and to become a methodology used by all as and when appropriate. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2364–2377, 2001     

Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus,nitrogen, and sulfur

A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.