Synthesis and characterization of hollow zeolite microspheres with a mesoporous shell by O/W/O emulsion and vapor-phase transport method

Hollow microspheres of ZSM-5 with a mesoporous shell have been synthesized through formation of amorphous hollow SiO₂/Al₂O₃ microspheres by sol–gel process in multiple oil–water–oil emulsions and transformation of the amorphous species into zeolite by water–organic vapor-phase transport treatment at 160 °C for 8 days. The morphology of the amorphous and zeolite spheres observed by scanning electron microscopy shows no significant change whereas the molar ratio of Si/Al increases from 6 to 20 during the transformation. The structural feature of zeolite was characterized by X-ray diffraction and ²⁹Si and ²⁷Al magic-angle spinning nuclear magnetic resonance. Transmission electron microscopy and N₂ adsorption–desorption isotherms indicate that uniform mesopores in the shell of zeolite spheres arise from the interstices among zeolite crystallites.     

Simultaneous synchrotron radiation X-ray diffraction-DSC analysis of melting and crystallization behavior of trilauroylglycerol in nanoparticles of oil-in-water emulsion

Crystallization, polymorphic transformation, and melting behavior of nanoparticles of trilauroylglycerol (LLL) in oil-in-water (O/W) emulsion were examined initially by DSC, and then by simultaneous synchrotron radiation small-angle (SAXS) and wide-angle (WAXS) X-ray diffraction and DSC (SR-SAXS /WAXS/DSC). The O/W nanoparticles emulsions having average diameters of 42 to 120 nm were prepared by application of mechanical shear using a high-pressure homogenizer. The following results were obtained: (i) The DSC study showed that the melting temperature of the stable β form of LLL was reduced from 46.7 (bulk) to 26.5–44.0°C (nanoparticles); this variation as assumed to be due to the size distribution of the nanoparticles. Crystallization temperature was also reduced from 18.9 (bulk) to −9.5±0.5°C (nanoparticles). These results were consistent with those of previous studies of nanoparticles of fats obtained in the O/W emulsion. (ii) The results obtained by the SR-SAXS/WAXS/DSC technique during the cooling process to −20°C showed that the first-occurring polymorph of LLL in the bulk liquid was β′, whereas α was first nucleated and transformed to β′ around −10°C during cooling in the nanoparticles. (iii) The SR-SAXS/WAXS/DSC data taken during the heating process from −20°C after the crystallization showed that β′ transformed to β around 0°C and that the melting of β started at 30°C and ended at 44°C. The present study showed that forming nanoparticles of LLL in the O/W emulsion having the diameters of 42 to 120 nm reduced the melting and crystallization temperatures and increased the transformation rate of α→β′→β in comparison to the LLL crystals formed in the bulk phase.     

Investigation of O/W emulsion separation and redispersion using fibrous PTFE bed coalescer

A series of fiber beds consisted of woven PTFE fiber mesh were used to investigate the influence of bed porosity (gradient porosity), permeability, specific surface area of bed, and superficial velocity on coalescence and separation process. It is found that too small bed porosity will not give better separation performance, for the reason of redispersion. The separation efficiency does not depend on the pore size but on the surface area of bed when the porosity is above 0.850. And a rapid drop of separation efficiency takes place above the porosity of 0.903. For effective separation of liquid droplets from a fluid stream, the gradient increasing porosity is the most favorable structure, which is effective to avoid redispersion of coalesced droplets.     

Effects of addition of diacylglycerols on fat crystallization in oil‐in‐water emulsion

The effects of addition of diacylglycerols (DAGs) on the crystallization behavior of n‐hexadecane dispersed in oil‐in‐water emulsion (oil 20% and water 80%, v/v) were studied by differential scanning calorimetry (DSC) and ultrasonic velocity measurement. In an attempt to modify the crystallization rate of n‐hexadecane, five DAGs having the fatty acid moieties of behenic (DAB), stearic (DAS), palmitic (DAP), lauric (DAL) and oleic acid (DAO) were added to n‐hexadecane, which was mixed with water and Tween 20 for emulsification. The DSC study showed that the addition of DAB, DAS or DAP (1.0 wt‐% with respect to n‐hexadecane) increased the crystallization temperature (Tc) of a n‐hexadecane/water emulsion from 3 °C (without DAG) to 8 °C, whereas the addition of DAL and DAO showed no effect. The ultrasonic velocity measurement also revealed that the addition of DAGs resulted in increasing the Tc of n‐hexadecane in O/W emulsion. These effects were discussed by taking into account the formation of molecular aggregates at the interface due to the addition of DAGs, which act as a template for crystallization of n‐hexadecane. The template‐assisted crystallization depends on the structure of the fatty acid chains present in the DAG: the longer the fatty acid moiety of DAG , the more is the crystallization of n‐hexadecane in O/W emulsion accelerated.     

毒死蜱农药的进展和剂型加工

毒死蜱是一种高效、广谱、低残留并有中等毒性的杀虫剂,可用于农业上粮食、蔬菜、水果及经济作物,防治50余种害虫,正成为替代甲胺磷等高毒农药的主要农药品种。本文论述毒死蜱农药国内外进展和剂型加工情况,指出改进毒死蜱乳油的方法以及研发毒死蜱水包油乳液剂型是替代毒死蜱乳油的方向。     

Complex formation in a ternary system composed of lauroamphoglycinate, oleic acid, and water

The formation of a complex, composed of lauroamphoglycinate (LG), oleic acid (OA) and water, was investigated, and this system was applied to emulsification. The complex was formed in the water-rich area (more than 90% in this system) at a molar ratio of OA to LG from 1 to 3, where two-phase systems of water and the complex existed. The interaction between LG and OA, both in the aqueous solution and at the interface of liquid paraffin dissolving the OA and LG solution, was studied by pH measurements and interfacial tension measurements, respectively. The results implied that LG and OA were linked stoichiometrically, both in aqueous solution and at the interface, and formed complexes. X-ray diffraction patterns and the strong hydrophobicity showed that the equimolar complex composed of LG, OA, and water was a liquid crystal with a reversed hexagonal structure. The reversed hexagonal liquid crystal was capable of solubilizing a certain amount of liquid paraffin in its alkyl group parts while maintaining its hexagonal structure. These results suggest the possibility to prepare a W/O-type emulsion by using the liquid crystal formed by LG, OA, partial liquid paraffin, and water as the continuous phase. The authors could obtain a stable W/O emulsion without coalescence of the water droplets that contained a substantial amount of water (approximately 90%). Furthermore, various types of emulsions, O/W, W/O, W/O/W, could be prepared by changing the ratio of LG and OA.     

Effects of hydrophobic emulsifier additives on crystallization behavior of palm mid fraction in oil-in-water emulsion

Ultrasonic velocity measurements and X-ray diffraction were employed to monitor the crystallization behavior of palm mid fraction (PMF) in oil-in-water emulsions (20 vol%). Three hydrophobic emulsifiers—sucrose oligoesters (SOE) containing palmitic acid (P-170) and stearic acid (S-170) moieties and a polyglycerine ester (DAS-750) containing a stearic acid moiety—were added to PMF in an attempt to increase the rate and extent of crystallization of PMF, which are otherwise suppressed owing to emulsification of the oil phase into many droplets. The results revealed that the hydrophobic emulsifiers accelerate the nucleation of PMF in the emulsion system, while retarding the rate of crystal growth. As a results, the crystallization temperature (T _c) of PMF increased with increasing concentrations of the hydrophobic emulsifiers. The effects of the three additives were different; in particular the addition of DAS-750 remarkably enhanced crystallization at low concentrations. By adding the emulsifiers at higher concentrations, the polymorphic behavior of PMF crystallization was also modified to different degrees, depending on the type of emulsifier. With addition of SOE, PMF crystallized predominantly in the β′ form; with addition of DAS-750, the extent of β′ nucleation was reduced by comparison with that observed with SOE. The results were explained in terms of adsorption of the hydrophobic emulsifier additives at the oil-water interface, which provides a template for acceleration of surface heterogeneous nucleation of PMF in the emulsion system.     

低粘度高固含量醋酸乙烯-丙烯酸酯共聚乳液胶粘剂的研制

介绍了一种低粘度、高固体含量的醋酸乙烯-丙烯酸丁酯-丙烯酸异辛酯共聚乳液胶粘剂的合成工艺及性能。该乳液粘度低于2500mPa.s,固体含量≥52%,较低的玻璃化温度和良好的耐水性能,应用于卷烟和防水涂料的生产。     

水性聚氨酯/聚甲基丙烯酸甲酯杂化乳液的合成

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)和二羟甲丙酸(DMPA)合成了水性聚氨酯分散体(WPU),讨论了PPG摩尔质量,NCO/OH及PPG/DMPA比例对WPU乳液和涂膜性能的影响。以WPU为种子与甲基丙烯酸甲酯进行乳液聚合制备杂化乳液,研究了不同PU/PMMA物质的量比例对杂化乳液及涂膜性能的影响,并采用TEM对WPU及杂化乳液粒子进行了表征。结果表明,在以PPG1000为原料,NCO与OH物质的量比为1.4∶1,PPG与DMPA物质的量比为1∶0.8条件下制备的WPU杂化乳液,随着PMMA比例增加,杂化乳液的稳定性和成膜性变差,聚合物膜断裂伸长率降低,但铅笔硬度、耐水性及耐乙醇性均得到了改善。     

复合可聚合乳化剂制备高固含量低黏度聚丙烯酸酯乳液

以DNS-86和F-6为复合可聚合乳化剂APS为引发剂,MMA、BA为单体采用半连续法制备20%固含量种子乳液,以种子乳液为介质,选用4种不同类型乳化剂:非离子可聚合乳化剂F-6,阴离子可聚合乳化剂DNS-86、常规非离子乳化剂OP-10、常规阴离子乳化剂SDS进行不同组合,同时滴加预乳化液、引发剂、缓冲剂直接二次成核制备62%固含量二元粒径分布乳液。重点研究了乳化剂复合方式、用量及配比、反应温度等对聚合稳定性、乳液流变性等的影响。,     

核壳型PVAc／PBA乳液的制备与表征

以醋酸乙烯酯（VAc）为核单体,丙烯酸丁酯（BA）为壳单体,二甲基丙烯酸乙二醇酯（EGDMA）为交联剂,采用分阶段饥饿态加料方式和半连续乳液聚合方法合成了具有硬核软壳结构的聚（醋酸乙烯酯／丙烯酸丁酯）。采用OP-10和十二烷基硫酸钠（SDS）质量比为2：1的复合乳化剂,用量为4％左右时乳液稳定;壳单体的滴加速度在5～6g／h时,聚合体系稳定,且转化率高。用FT—IR分析了聚合物的结构;并用透射电镜表征了乳胶粒结构。     

Demulsification of oil-in-water emulsion under freezing conditions: Effect of crystal structure modifier

The demulsification of oil-in-water (O/W) emulsions under freezing conditions is connected to fat crystallization in the oil droplet. Therefore, demulsification can be prevented by the use of oil with a low melting point, and also by lowering the O/W ratio. However, an oil with a low melting point, such as sunflower, is rather expensive, and the O/W ratio has a significant effect on the texture of emulsions. We searched for an oil that is suitable for the production of a freeze-stable emulsion and found that soybean oil has unique characteristics. Normally, emulsions are more unstable at lower temperatures; soybean oil emulsion is unstable at −10°C and stable at −20°C. This unique characteristic results from the following two reasons. First, the solid fat content of soybean oil is almost the same at −10 and −20°C. Second, small crystals form a larger network over a period of time, and the higher temperature promotes faster restructuring. This structure formation was microscopically observed with the use of a thermostated stage. Structure formation was suppressed with the addition of a crystal structure modifier, polyglycerol fatty acid full ester, which also suppressed coalescence.     

Novel evaluation method for the water- in- oil (W/O) emulsion stability by Turbidity Ratio Measurements

The turbidity ratio method of evaluating the stabilities of water-in-oil emulsions has been established with two wavelengths (450 and 850 nm) by taking the intensity ratio of two beams. The slopes of turbidity ratio of several water-in-oil emulsions with time were calculated to evaluate the emulsion stabilities at different HLB (Hydrophilie-Lipophile Balance), the amounts of emulsifiers, and water contents. The results of the turbidity ratio technique were consistent with the amount of phase separation of emulsions incubated for 30 days at room temperature. From the turbidity ratio measurements, we determined that the required HLB of diesel oil was about 6.0, and that the stability of emulsion increased with the amount of emulsifier. The increasing amount of the water showed a negative effect on emulsion stability. Finally, this method provides a useful tool for the quick evaluation of the required HLB and the condition of emulsification throughout this study.     

EELFS as a new tool of local structural characterization of solid surfaces

A new apparatus to obtain information on local structures and chemical states of solid surfaces has been constructed, with which we measure electron energy-loss fine structures (EELFS), excited by electrons of a few keV incident at a grazing angle. We describe results about O/Ni(100) and O/W(100) systems, where we extensively take advantage of anisotropy in regard to momentum transfer of the probe electron and high surface sensitivity of this technique.     

醋酸乙烯酯与叔碳酸乙烯酯共聚乳液(W乳液)的研制

摘要用叔碳酸乙烯酯(Veova10)单体对醋酸乙烯酯乳液进行改性,采用种子聚合的方法,以过硫酸钾为引发剂,使用阴离子和非离子复配的乳化剂,加入一定量的丙烯酸酯类单体,可制得耐碱性、耐水性、耐候性都非常好的乳液。此共聚乳液特别适合用作内墙和外墙乳胶漆的基料。     

Magnetite/poly(D,L-lactide-co-glycolide) and hydroxyapatite/poly(D,L-lactide-co-glycolide) prepared by W/O/W emulsion technique for drug carrier: Evaluation of in vitro release of dexamethasone from composite nanoparticles

Biocompatible polymeric carriers containing inorganic materials for delivering therapeutic agents to a targeted site are promising candidate for drug delivery. Two nanocomposite nanoparticles, magnetite/poly(D,L-lactide-co-glycolide) and hydroxyapatite/poly(D,L-lactide-co-glycolide) (Fe₃O₄/PLGA and HAp/PLGA, respectively), with different weight ratios of inorganics to polymer and different polymer molecular weights were prepared by water-in-oil-in-water (W/O/W) emulsion technique to determine incorporation and in vitro release profile of the small molecule drugs water-insoluble dexamethasone acetate (DEX-Ac) and water-soluble dexamethasone phosphate (DEX-P). The in vitro release for DEX-Ac nanoparticles showed an initial burst release followed by a continuous slower release, whereas DEX-P nanoparticles showed only rapid initial release behavior.     

水基性农药制剂的开发和前景

论述了水基性农药制剂的内容和类型,详细地讨论了悬浮剂、水乳剂和微乳剂水基性制剂的开发、优劣和前景。指出微乳剂在国际上不是剂型开发的趋势,国内开发微乳剂应审慎对待;而开发悬浮剂和水乳剂的水基性制剂是更有利和有前景的。     

Encapsulation of TiO2 by emulsion polymerization with methyl metacrylate (MMA)

Summary This paper presents a methodology of encapsulation of TiO₂ (Titanium dioxide) by emulsion polymerization on the proposal to modify the physical-chemical properties of the pigment surface. In the proposed methodology the TiO₂ was previously modified by isopropoxy-titanium-tri-isostearate, before being encapsulated by emulsion polymerization using Methyl Methacrylate as monomer. The effects of the polymerization process, type of initiator and monomer concentration in the efficiency of encapsulation were studied. The encapsulated pigment was characterized by Thermogravimetric Analysis (TGA), Light Scattering (LS) and Transmission Electron Microscopy (TEM).     

聚氨酯-丙烯酸酯（PUA）复合乳液的研究进展

综述了聚氯酯-丙烯酸酯(PUA)复合乳液的制备方法,研究新进展及其应用。     

Characterization of grafting in the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as stabilizer

Emulsion polymerizations of vinyl acetate (VAc) with polyvinyl alcohol (PVA) as emulsifier were carried out by both batch and semicontinuous processes. The extent of grafting of vinyl acetate onto the PVA chains was investigated by a new method for separating the various polymer fractions in high solids content latexes. The quantification was carried out by a three‐step separation and selective solubilization of the PVAc latexes. After the separation, the water‐soluble PVA and the solvent‐soluble PVAc components were characterized by gel permeation chromatography and ¹³C–NMR, from which the accuracy of this method was verified. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1739–1747, 2001