Synthesis and Characterization of Hydrogel Nanoparticles Through Inverse Microemulsion Polymerization of 2-Acrylamido-2-methyl-1-propanesulfonic Acid

Nanosized hydrogel particles prepared through inverse microemulsion polymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid, using the combination of an oil soluble emulsifier (SPAN80) with a water soluble emulsifier (TWEEN 80), and precise determination of HLB range related to the formation of stable single phase microemulsions.

The effect of crosslink density, water phase to oil phase ratio, and the hydrophilic-lipophilic balance (HLB) value on polymerization rate, particle size, and swelling ratio were investigated. It found that polymerization rate and particle size are strongly dependent on the water phase to oil phase ratio. Hydrogel samples prepared using oil soluble and water soluble initiators and the results showed that the initiator type had a great influence on monomer conversion and particle size. Effect of pH on equilibrium swelling of hydrogels was studied by dynamic light scattering and hydrogels showed pH-independent swelling behavior in a broad range of pH values. We also reported and discussed the crosslink density distribution in nanogels prepared by inverse microemulsion polymerization.     

聚苯乙烯-甲基丙烯酸甲酯功能微球的合成

本文研究了在用乳液聚合法合成苯乙烯/甲基丙烯酸甲酯共聚功能微球过程中,乳化剂、电解质、油水比、溶剂等因素对共聚胶乳微粒的粒径大小和粒度分布的影响。结果表明,乳化剂的种类和浓度对生成胶乳微粒的粒径有很大影响,且胶乳微粒的粒径随电解质浓度的增加以及油水比的减小而减小,加入溶剂可明显提高所得微粒的粒径。     

Microemulsion polymerization of butyl acrylate. IV. Effect of emulsifier concentration

The oil/water microemulsion polymerizations of butyl acrylate initiated by a water (ammonium peroxodisulfate, APS) or oil (dibenzoyl peroxide, DBP) soluble radical initiator at different emulsifier concentrations were investigated. The rate of polymerization vs. conversion curve shows two intervals. The rate of polymerization is found to decrease with the emulsifier concentration. This finding was discussed in terms of the decrease of both radical and monomer concentration, the chain transfer to emulsifier, desorption of chaintransferred radicals, and the contribution of solution polymerization. The polymerization is faster with APS. In the APS system the rate per particle or the number of radicals per particle increases exponentially with increasing particle size. The particle size and number increase during the whole polymerization. This behavior was discussed in terms of the nucleation of monomer-containing micelles and agglomeration of primary particles during the whole polymerization. © 1995 John Wiley & Sons, Inc.     

明胶微球粒径控制的研究

采用乳化-凝聚法,在油包水(w/o)的体系中对明胶微球(GMs)粒径、微球的形态和分散性等进行了研究.扫描电子显微镜(SEM)和粒径分布曲线的结果表明在乳化体系中,提高明胶溶液的浓度或水油比例,明胶微球的粒径增大;增加乳化剂的用量,微球的粒径减小;选择合适的乳化时间和搅拌速率,可以改善微球的分散性和表面光滑程度.同时,通过调控实验条件,在明胶溶液浓度0.100 g/mL,水油比1/5,乳化剂浓度0.05g/mL时研制出了平均粒径为3.58μm的表面光滑、分散性好的明胶微球.     

STUDY ON THE POLYMERIZATION KINETICS AND STABILITY OF P(UA)/MMA MICROEMULSION*

 Urethane acrylate anionomer (APUA) as a kind of new type polymerizable emulsifier was synthesized using 2,4-toluene diisocyanate (TDI), polypropylene glycol (PPG), 2-hydroxyethyl methacrylate (HEMA) and dimethylolpropionic acid (DMPA). The critical micelle concentration (CMC) of APUA was measured by the methods of conductance and surface tension. The comparative studies between polymerizable emulsifier AUPA and conventional emulsifier sodium dodecyl sulfate (SDS) were carried out in the emulsion polymerization of methyl methacrylate (MMA). Polymerization kinetics,stability, size and morphology of the latex particles were investigated. It was found that in APUA both water soluble initiator potassium persulfate (KPS) and oil soluble initiator 2,2'-azobisisobutyronitrile (AIBN) can start the reaction of MMA, and the polymerization rate and yield were very high. On using AIBN as an initiator, the conversion-time behavior of MMA with APUA as emulsifier was different to that of SDS as emulsifier, signifying a different nucleation mechanism of the polymer latex particle. The average size of the two kinds of particles is about 50 nm. The particle size decreases with increasing emulsifier concentration. On using KPS as the initiator, APUA as emulsifier, cross-linking hydrogel of PMMA would be formed, but SDS was used as emulsifier and the hydrogel of PMMA was not present.     

Premix Membrane Emulsification: Preparation and Stability of Medium-Chain Triglyceride Emulsions with Droplet Sizes below 100 nm

Premix membrane emulsification is a promising method for the production of colloidal oil-in-water emulsions as drug carrier systems for intravenous administration. The present study investigated the possibility of preparing medium-chain triglyceride emulsions with a mean particle size below 100 nm and a narrow particle size distribution using sucrose laurate as an emulsifier. To manufacture the emulsions, a coarse pre-emulsion was repeatedly extruded through alumina membranes (Anodisc^™) of 200 nm, 100 nm and 20 nm nominal pore size. When Anodisc^™ membranes with 20 nm pore size were employed, nanoemulsions with z-average diameters of about 50 nm to 90 nm and polydispersity indices smaller than 0.08 could be obtained. Particle growth due to Ostwald ripening was observed over 18 weeks of storage. The Ostwald ripening rate linearly depended on the emulsifier concentration and the concentration of free emulsifier, indicating that micelles in the aqueous phase accelerated the Ostwald ripening process. Long-term stability of the nanoemulsions could be achieved by using a minimised emulsifier concentration or by osmotic stabilisation with soybean oil added in a mass ratio of 1:1 to the lipid phase.     

环氧树脂水基分散体系的相反转乳化

以聚乙二醇－邻苯二甲酸酐－环氧树脂Ｅ－４４多元嵌段共聚体为乳化剂,将环氧树脂Ｅ－４乳化成水包油的稳定水基乳液。用乳液体系电导率和粘度的变化表征了相反转乳化过程。研究了乳化剂浓度、三元多嵌段共聚体中亲水嵌段分子量和乳化温度对相反转乳化过程的影响。实验结果表明,体系在较高乳化剂浓度（９．１％）下为完全相反转,在低乳化剂浓度（４．１％）下为不完全相反转。相反转时水与环氧树脂Ｅ－４４的重量比值随乳化剂浓度     

乳化剂分子亲水组分含量对相反转乳化过程的影响

高分子树脂水基分散体系 ,因其结构的可灵活调节性 ,在许多方面得到应用 ,又因其不含有机溶剂 ,能完全满足环境保护和生态的要求而备受关注 [1～ 3] .相反转乳化技术是制备高分子水基体系的新方法 ,它适用于制备包括加聚物和缩聚物的大多数高分子水基体系 ,大大拓宽了水基体系的范围 [4 ] .杨振忠等[5] 利用自己合成的高分子非离子型乳化剂将环氧树脂乳化成微粒尺寸小且分布窄的水基分散体系 ,对相反转机理和相反转技术进行了深入研究 .研究表明 ,乳化剂浓度和乳化温度对相反转后水基微粒尺寸和形态有重要影响 ,高乳化剂浓度和较低的乳化温…     

Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation

The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of free emulsifier for additional nucleation. In the mixed ionic/non-ionic emulsifiers, the released non-ionic emulsifier can displace the ionic emulsifier at the particle surface, which then takes part in additional nucleation. The non-stationary state polymerization can be induced by the addition of a small amount of ionic emulsifier or the incorporation of ionic groups onto the particle surface. Considering the ionic sites as no-adsorption sites, the equilibrium adsorption layer can be thought of as consisting of a uniform coverage with holes. The de-organization of the interfacial layer can be increased by interparticle interaction via extended PEO chains--a bridging flocculation mechanism. The low overall activation energy for the sterically stabilized emulsion polymerization resulted from a decreased barrier for entering radicals at high temperature and increased particle flocculation.     

Polymerization of acrylamide in nonionic microemulsions: Characterization of the microlatices and polymers formed

Free radical polymerization of acrylamide was carried out in nonionic microemulsions of water, an isoparaffinic oil, Isopar M and a blend of nonionic emulsifiers: a sorbitan sesquioleate and a polyoxyethylene sorbitol hexaoleate (HLB of the mixture: 9.3). The size and the stability of the latex particles formed after polymerization were studied as a function of monomer, emulsifier and electrolyte concentration. High emulsifier and high monomer contents favor obtaining high molecular weight polyacrylamides. It is shown that both the number of polymer chains contained in each latex particle and the size of the particles are essentially controlled by the acrylamide/emulsifier weight ratio.     

Temperature-induced phase separation in pseudoternary mixtures of Triton X-100–butanol–kerosene–water

The transparent Winsor IV domain in the phase diagram of the mixtures of emulsifier (Triton X-100 and butanol), oil (kerosene), and water is found to be 34% of the total phase diagram in presence of emulsifier with surfactant:cosurfactant::1:1, and is water dominant. Increase in cosurfactant/surfactant ratio inverts the Winsor IV domain to become oil rich. The plot of conductance of the microemulsions prepared by substituting water by brine against water content depicts the existence of three distinct phases like oil-in-water, bicontinuous, and water-in-oil microemulsion in the phase diagram. The phase contrast micrographs of the mixtures of different compositions in these three different phases reveal the existence of microdroplets of oil dispersed in water and water dispersed in oil. Further, the dynamic light scattering studies of these solutions reveal an inhomogeneity in the size distribution of the droplets. A temperature-induced clouding in the microemulsion domain leading to phase separation has been observed. Additives like glucose, sucrose, and sodium chloride decrease the cloud point (CP), while addition of ammonium thiocyanate increases it. A quantitative relationship of the clouding temperature with the composition of the microemulsion has been established. With increase in oil and emulsifier, the cloud point of the microemulsion increases. The separated phases after the clouding have been used for preconcentration of water-soluble metal ions as well as oil-soluble dyes. The turbid systems on heating led to separation into three isotropic phases which are found to be stable at ambient temperature. The stability of these phases is ascribed to the formation of stable microemulsions by mass transfer from one phase to other.     

反相乳液共聚合制备两性丙烯酰胺共聚物的研究

采用Span80-Tween80复合乳化剂和AIBA引发剂,进行丙烯酸钠(NaAA)/丙烯酰胺(AM)/丙烯酰氧基乙基三甲基氯化铵(DAC)反相乳液共聚合.研究了聚合温度、引发剂用量、单体浓度、共聚单体中DAC和AM含量、乳化剂用量及其HLB值、水/油比和水相pH值等聚合反应工艺条件或参数对聚合反应单体转化率和聚合物特性粘度的影响,聚合物特性粘度随引发剂用量和单体浓度的增大而增大的实验结果证实了该两性丙烯酰胺共聚物反相乳液制备过程中凝胶效应的存在.傅立叶红外光谱组成分析表明了两性丙烯酰胺共聚物的成功合成,扫描电镜观测乳胶粒粒径范围在0.6~8.0μm.     

Competitive solubilization of cholesterol and phytosterols in nonionic microemulsions studied by pulse gradient spin-echo NMR

The actual mechanism of cholesterol reduction by phytosterols is yet to be explored. One hypothesis states that cholesterol and phytosterols compete on the solubilization locus within gastric bile salt micelles. In this study competitive solubilization within microemulsions as vehicles for dietary intake of cholesterol and phytosterols was studied by pulse gradient spin-echo nuclear magnetic resonance. The loaded microemulsions undergo phase transitions as a function of dilution, the type of solubilized sterol, and the weight ratio of the cosolubilized sterols. Microemulsions containing 10-20 wt% of aqueous phase, show similar diffusivity of the oil and aqueous phases in all examined systems (excluding PS-loaded one) reflecting the minor influence of these solubilizates on the structure of the inner and the outer phases. The closeness of these structures enables the mobility of water molecules between them. Upon further dilution (>20 wt% aqueous phase), significant differences in decrease rate of the oil and increase of the water phases mobilities (occurring upon inversion), were detected within the studied systems. It was concluded that the solubilized sterols influence the structural transitions based on their location within the structures and their competitive solubilization. The phytosterols solubilized mostly in the continuous oil phase and between the surfactant tails. Cholesterol is solubilized in the vicinity of the surfactant headgroups and affects the surface curvature. In mixtures of cholesterol and phytosterols, structural changes are dictated mostly by the presence of the cholesterol.     

Evaluation of polymeric flocculants for oily water systems using a photometric dispersion analyzer

During oil production and treatment, oil-in-water (O/W) emulsions are formed. These dispersions require treatment prior to disposal. In order to improve oil/water separation processes through any physical process (decanting, flotation, centrifuging etc), the particle size of the dispersed phase should be increased. This may be obtained by a flocculation process, which consists in the agglomeration of several particles or drops using as flocculating agent hydrophilic high molecular weight macromolecules. Poly (ethylene-b-propylene oxide) and poly (vinyl alcohol) polymers have been evaluated as flocculating agents for oily water systems. Their performance is related to the particle size increase of the dispersed phase. In this work, a photometric dispersion analyzer (PDA) has been used to accomplish the oil drop agglomeration. Synthetic as well as produced water was used. Data are in good agreement with previous tests. Qualitative information related to aggregates or particle size distribution of the oily water systems can be obtained using PDA.     

生物基表面活性剂七叶皂素的界面行为

以天然三萜皂苷七叶皂素为研究对象, 分别采用吊片法、 悬滴法和高速摄像机动态拍摄法探究了七叶皂素分子在气-液、 液-液、 固-液界面的界面行为. 考察了以七叶皂素为乳化剂制备乳液的性质, 以及七叶皂素对液滴在疏水固体表面润湿铺展行为的调控规律, 并从分子层次角度分析了作用机理. 结果表明, 七叶皂素能在气-液界面发生吸附, 将水的表面张力降低至42.1 mN/m, 临界胶束浓度为5×10^?4 mol/L. 七叶皂素还可以在油-水界面吸附, 将亲油端插入油相, 亲水端插入水相, 形成稳定的界面膜, 降低界面张力. 以七叶皂素为乳化剂所制备的乳液, 随着浓度增大可以达到较小的粒径和较大的Zeta电势, 短时间内表现出较好的稳定性. 高浓度的七叶皂素可以很好地抑制液滴在疏水固体表面的弹跳和回缩, 达到很好的铺展效果, 有利于拓展其在诸多领域的应用.     

Some aspects of stability of multiple emulsions in personal cleansing systems

The two dominant factors that were found to affect the stability of multiple emulsions in high HLB surfactant systems are the osmotic pressure imbalance between the internal aqueous phase and the external aqueous phase, and the adsorption/desorption characteristics of the emulsifier/surfactant film at the oil/water interface. Synergistic interaction between the low HLB emulsifier and the high HLB surfactant that produces very low interfacial tension of the order of 10(-2) mN/m at the oil/water interface was found to occur in some of the systems investigated. Long term stability was observed in multiple emulsion containing these systems. However, no synergy was observed in systems in which either the oil or the emulsifier, or both, contained unsaturated chains. In fact, desorption of the adsorbed surfactant film was observed in systems containing unsaturated chains. The observed desorption from the interface of the emulsifier in these systems was attributed mainly to the inability of the unsaturated chains to form a close packed, condensed interfacial film. Presence of closely packed, condensed interfacial film is necessary to prevent solubilization of the adsorbed low HLB emulsifier by the high HLB surfactant. Multiple emulsions prepared using systems containing unsaturated hydrocarbons were highly unstable.     

MULTIPLE EMULSIONS. PART II: PROPOSED TECHNIQUE TO OVERCOME UNPLEASANT TASTE OF DRUGS

Multiple emulsions of water in oil in water (W/O/W) have been used as a novel technique to overcome unpleasant taste of drugs. The drug is dissolved in the inner water phase and is released throughout the oil phase in the presence of synthetic gastric juice

Yield of preparation and stability have been studied using various sets of different inner (emulsifier I) and outer (emulsifier II)emulsifiers

Combination of anionic-nonionic emulsifiers yielded optimal results: High yield of preparation, high stability and complete release of the drug in synthetic gastric juice.     

颗粒乳化剂的研究及应用

近年来,颗粒乳化剂因其在食品、采油、化妆品、医药、催化以及功能纳米材料制备等领域具有潜在应用前景而备受关注。本文综述了近来颗粒乳化剂的研究进展,归纳了颗粒乳化剂的种类,包括:无机纳米粒子、表面改性或杂化的无机粒子、有机纳米粒子以及特殊的颗粒乳化剂Janus粒子;并对颗粒乳化剂能够在油水界面稳定吸附的热力学机理和动力学行为进行了阐述,颗粒乳化剂在油水界面接触角以及粒径大小是其在界面稳定吸附的关键参数,而颗粒在油水界面的排布方式则主要受粒子之间相互作用的影响。重点介绍了颗粒乳化剂的热点应用,包括:(1)利用颗粒乳化剂制备Pickering乳液,以及通过对颗粒乳化剂的功能化,使得Pickering乳液具备环境响应性(即pH、盐浓度、温度、紫外光、磁场敏感响应性);(2)以颗粒乳化剂为构筑基元、以Pickering乳液为模板制备Janus颗粒、Colloidosome、具有多级结构的粒子或膜,以及多孔结构材料;(3) Janus粒子在催化领域的应用。     

Hydroxyapatite nanoparticles as stimulus-responsive particulate emulsifiers and building block for porous materials

Hydroxyapatite (HAp) nanoparticles with spherical, rod-shaped or fiber-shaped morphologies were synthesized by wet chemical method in aqueous media. Scanning electron microscopy, dynamic light scattering, helium pycnometry, and aqueous electrophoresis techniques were used to characterize the nanoparticles in terms of their particle size and morphology, density and zeta potential, respectively. Stable "Pickering-type" emulsions were prepared using the HAp nanoparticles as a particulate emulsifier and methyl myristate as an oil phase above pH 7.7, but not below pH 6.1. These emulsions were characterized in terms of their emulsion type, mean droplet diameter and morphology using electrical conductivity, light diffraction and optical microscopy. Rapid demulsification could be induced by lowering the solution pH: addition of acid led to dissolution of the HAp nanoparticles attached on oil-water interface and the emulsion was destabilized. HAp nanoparticles precipitated by addition of base to the aqueous phase after demulsification and the HAp particles precipitated worked as an effective particulate emulsifier. This emulsification-demulsification cycle was reversible. Sintering of methyl myristate-in-water emulsion stabilized with the HAp nanoparticles led to a porous HAp material.     

Incorporation of water-soluble drugs in PLGA microspheres

Poly(lactide-co-glycolide) (PLGA) microspheres containing blue dextran, as a model of water-soluble drugs, were prepared from w₁/o/w₂ emulsions by using a microhomogenizer and a solvent evaporation method. Effects of preparation conditions, such as, concentration of poly(vinyl alcohol) (PVA) in w₂ phase, viscosity of inner soluble water phase, volume ratio of oil phase to w₁ phase in primary emulsion, PLGA concentration in oil phase, and molecular weight or composition of PLGA, upon the properties of PLGA microspheres containing water-soluble drugs were examined. Concentration of poly(vinyl alcohol) (PVA), the dispersant dissolved in w₂ phase of secondary emulsion did not show any effects on the final particle size. On the other hand, volume ratio of oil phase to water one in primary emulsion affected the final particle size, which seemed to be related to the local PLGA concentration in w₁/o emulsions. That is, the particle size increased as the volume ratio of w₁ phase against oil phase, w₁/o (v/v), increased. The loading efficiency, however, was not affected by the volume ratio of w₁/o (v/v), but affected by blue dextran concentration in w₁ phase. Higher loading efficiency was observed in PLGA microspheres prepared from w₁ phase containing lower concentration of blue dextran. Blue dextran solution (inner water phase) with the lower viscosity may result in the lower leakage ratio of blue dextran during the preparation procedure. Increases in concentration and molecular weight of PLGA made particle size larger.