调酸介质对二甲戊灵微胶囊囊形及粒径的影响

[目的]优选出原位聚合法制备二甲戊灵微胶囊的较佳调酸介质,为二甲戊灵的微胶囊化提供一定的理论指导.[方法]以脲醛树脂为壁材采用原位聚合法制备了二甲戊灵微胶囊,研究了不同调酸介质对二甲戊灵微胶囊囊形及粒径的影响.[结果]5％盐酸溶液作为调酸介质形成的微胶囊囊形粗糙,产生粘连,粒径分布较宽;5％硝酸铵溶液、5％硫酸氢铵溶液作为调酸介质形成的微胶囊囊形松散,容易破裂,产生粘连,粒径分布较窄;5％氯化铵溶液作为调酸介质形的微胶囊囊形光滑致密且坚固,粒径分布较窄.[结论]调酸介质对原位聚合法制备的微胶囊囊形及粒径影响很大,选择合适的调酸介质能获得囊形致密、粒径分布窄的微胶囊.     

压敏显色微胶囊及其涂料的研究进展

综述了无碳复写纸的结构类型和性能、压敏显色微胶囊制备及其微胶囊涂料的最新进展。揭示了微胶囊技术在无碳复写纸应用中的重要作用。     

压敏型粘合剂用微胶囊的研制

原位聚合法制备以溶剂油为囊芯,尿素-三聚氰胺-甲醛树脂为囊壁的微胶囊,采用高剪切混合乳化机对芯材进行乳化,脲-甲醛量比2：1,先碱性后酸性的缩聚反应工艺,添加系统改性剂,得到粒径在10～20μm的占93%、包埋率较高、囊壁光滑致密的微胶囊。应用于制备压敏型微胶囊粘合剂,储存稳定,性能优越,使用方便。     

响应面法优化微胶囊复合壁材配比的研究

壁材作为微胶囊的重要组成部分,决定微胶囊的特性。本文选择海藻酸钠等为壁材,采用高压静电微胶囊制备装置,以成囊合格率为检测指标,运用Box-Behnken中心组合设计和响应面分析,研究了壁材配比对微胶囊特性的影响。得到的最优壁材配比为1.53%海藻酸钠,4.52%聚乙烯醇,1%明胶,1%甘油,成囊溶液氯化钙浓度为22.86g/L,微胶囊合格率为87.37%。可为食品、医药、化工等微胶囊化壁材配比选择提供参考。     

丹参酮的微胶囊化

将丹参酮溶解于肉豆蔻酸异丙酯后，采用明胶／阿拉伯胶为壁材，使用复合凝聚法对其进行了微胶囊化，研究了多种反应条件对丹参酮／肉豆蔻酸异丙酯微胶囊化的影响。结果发现，壁材和芯材的组成比例对微胶囊的包埋率有较大的影响；搅拌速度的增加会使微胶囊的粒度变小；表面活性剂的加入会使微胶囊的粒度分布变窄。在合适的条件下，制备得到的微胶囊产品包埋率可达80％以上，平均体积粒度可达几十微米。     

响应面法优化微胶囊复合壁材配比

采用高压静电微胶囊制备装置,以成囊合格率为检测指标,选择海藻酸钠等为壁材,运用Box-Behnken中心组合设计和响应面分析,研究了壁材配比对微胶囊特性的影响。得到的最优条件是:壁材组成为质量分数1.53%(以下都是质量分数)海藻酸钠,4.52%聚乙烯醇,1%明胶,1%甘油,成囊溶液氯化钙质量浓度为22.86g/L,微胶囊合格率为87.37%。在最优条件下制备出的微胶囊内外表面光滑,囊壁透明,分散性好,形态完整。可为食品、医药、化工等微胶囊化壁材配比选择提供参考。     

原位聚合法制备脲醛树脂包覆环氧树脂微胶囊

以脲醛树脂为囊壁、环氧树脂E-51的乙酸乙酯溶液为囊芯,采用原位聚合法成功制备了脲醛树脂包覆环氧树脂溶液的微胶囊。通过改变尿素、甲醛、芯材用量等研究了脲醛树脂生成速率和沉积速率对微胶囊形貌和结构的影响。利用扫描电子显微镜、光学显微镜、傅里叶变换红外光谱仪和热重分析仪对微胶囊进行表征。结果表明:成功制备了外表面粗糙和光滑的两种微胶囊,且这两种微胶囊的芯材都具有良好的流动性;外表面粗糙的微胶囊力学性能较好,热稳定性优良。     

静电自组装法制备阿维菌素微胶囊

以磺化碱木质素聚氧乙烯醚(SAL-PEG)/聚乙烯亚胺(PEI)为壁材,阿维菌素原药为芯材,采用静电自组装法制备了木质素基阿维菌素微胶囊(AVM-CS)。考察了芯壁比(芯材与壁材的质量比)、交联剂用量、交联反应pH、NaCl溶液浓度对微胶囊成囊性能和缓释性能的影响,得到最优AVM-CS成囊条件为:芯壁比为2∶5、戊二醛用量为4%(戊二醛质量占壁材质量的百分比,下同)、壁材发生交联时的反应液pH=8,在1 mol/L NaCl溶液中成囊。制备的AVM-CS呈不规则球状,粒径范围1~5μm。缓释性能测定结果发现,以AVM-CS与聚氨酯为壁材制备的阿维菌素微胶囊(PU-CS)的缓释效果相当,AVM-CS的原药累积释药量大于93%,高于87%的PU-CS的原药释药量。     

过氧化苯甲酰微胶囊的制备与应用

以尿素、三聚氰胺和甲醛的预缩合物为壁材,过氧化苯甲酰为囊芯,采用原位聚合的方法制备了过氧化苯甲酰微胶囊。讨论了在过氧化苯甲酰微胶囊形成过程中不同种类的润湿分散剂及其用量、酸的加入速度等对微胶囊状态及粒径分布的影响,通过大量对比实验,得出制备过氧化苯甲酰微胶囊的最佳反应条件、适宜的分散剂及用量。同时,通过相关的胶黏剂配方试验表明,将制备的微胶囊应用于螺纹锁固厌氧胶中,取得良了好的效果,能够很好满足客户的技术要求。     

磺化碱木质素聚氧乙烯醚/聚乙烯亚胺静电自组装法制备阿维菌素微胶囊

以磺化碱木质素聚氧乙烯醚（SAL-PEG）/聚乙烯亚胺（PEI）为壁材,阿维菌素原药为芯材,采用静电自组装法制备了木质素基阿维菌素微胶囊（AVM-CS）。分别研究芯壁比、交联剂的用量、交联反应pH、NaCl溶液浓度等因素对微胶囊成囊性能和缓释性能的影响,确定优化的AVM-CS成囊参数为：芯壁比=2/5、戊二醛用量=2%、交联pH=8,在1 mol/L NaCl溶液中成囊。制备的AVM-CS呈不规则球状,粒径范围为1~5μm。缓释性能研究发现AVM-CS与聚氨酯壁材制备的阿维菌素微胶囊的缓释效果相当,但是AVM-CS的释放比较完全,原药的利用率更高。     

Chitosan nanoparticles as particular emulsifier for preparation of novel pH-responsive Pickering emulsions and PLGA microcapsules

In this work, we describe a novel and simple method for fabricating biocompatible microcapsules. Chitosan colloidal nanoparticle-coated micrometer-sized poly(lactic-co-glycolic acid) (PLGA) microcapsules were fabricated via a combined system of “Pickering-type” emulsion route and solvent volatilization method in the absence of any molecular surfactants. Stable oil-in-water emulsions were prepared using chitosan colloidal nanoparticles as a particulate emulsifier and a dichloromethane (CH₂Cl₂) solution of PLGA as an oil phase. Moreover, this stable emulsion present a good pH-responsive characteristic. The uncross-linked chitosan nanoparticles coated PLGA microcapsules were fabricated by the evaporation of CH₂Cl₂ from the emulsion, and the cross-linked chitosan nanoparticles coated PLGA microcapsules were prepared by cross-linking with glutaraldehyde and evaporation of CH₂Cl₂. The two types of microcapsules were characterized in terms of size, morphology using scanning electronic microscope (SEM), optical microscope, and so on. These observations confirm the robust nature of these cross-linked microcapsules. Moreover, a possible mechanism for the formation of these microcapsules was proposed. The combined system of Pickering emulsion and solvent volatilization opens up a new route to fabricate a variety of microcapsules.     

Microencapsulation of water‐soluble herbicide by interfacial reaction. I. Characterization of microencapsulation

A new microencapsulation was established in which small microcapsules with a hydrophilic polymeric wall could be fabricated, capsulizing the water‐soluble content. The new microencapsulation is based on an emulsion interfacial reaction technique that combines the characteristics of an interfacial reaction and conventional emulsion processes. In this technique, hydrophilic polymers [poly(vinyl alcohol) and chitosan] were used as the wall material of the microcapsules. The microencapsulation process was composed mainly of the following steps: preparation of a water/oil (w/o) emulsion 1 containing hydrophilic polymers and a water‐soluble core material and w/o emulsion 2 containing a water‐soluble crosslinking agent and catalyst; the formation of microcapsules by mixing emulsion 1 and emulsion 2; and washing and drying the formed microcapsules. In the new technique an insoluble polymer film was formed easily by the fast crosslinking reaction on the surface of tiny emulsified polymer solution particles in contact with the emulsified crosslinking agent solution particles under mixing with high speed agitation. Thereby, small stable microcapsules were formed. The emphasis in this study was on the establishment of the microencapsulation process by which microcapsules were formed and controlled. The microencapsulation was characterized by analysis of the size distribution of microcapsules fabricated with process conditions. The clarification of the effect of the preparation conditions was also made on the morphology and diameter of the microcapsules. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1645–1655, 2000     

Structural control of core/shell polystyrene microcapsule‐immobilized microbial cells and their application to polymeric microbioreactors

Polystyrene microcapsules possessing a large single core and highly microporous wall were prepared as immobilization supports for microbial cells by a new method based on phase separation of polystyrene within a mixed organic solvent system in an oil‐in‐water (o/w) emulsion. The structures of core and micropore were controlled by changing the concentration of isooctane in the organic phase and the temperature of solvent evaporation. The immobilization of baker's yeast into the polystyrene microcapsules was carried out by entrapping the yeast into calcium alginate beads before encapsulating in the microcapsules and followed by removing the beads with HCl solution. The morphology of the microcapsules was observed by means of SEM, and the activity of the immobilized yeast was evaluated by using the microcapsules in ethanol fermentation. It was found that the formation of the core and wall pore was remarkably influenced by the isooctane concentration, and the diameter of the core was affected by the temperature of solvent evaporation. The yeast was successfully immobilized into the polystyrene microcapsules at a high density and a high catalyst activity by the proposed immobilization method. Furthermore, the polystyrene microcapsules exhibited a high operational stability in the repeated batchwise fermentation test. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1966–1975, 2003     

Suspension polymerization based on inverse Pickering emulsion droplets for thermo-sensitive hybrid microcapsules with tunable supracolloidal structures

Polymerization using Pickering emulsion droplets as reaction vessels is being developed to become a powerful tool for fabrication of hybrid polymer particles with supracolloidal structures. In this paper, two kinds of thermo-sensitive hybrid poly(N-isopropylacrylamide) (PNIPAm) microcapsules with supracolloidal structures were successfully prepared from suspension polymerization stabilized by SiO₂ nanoparticles based on inverse Pickering emulsion droplets. SiO₂ nanoparticles could self-assemble at liquid-liquid interfaces to form stable water-in-oil inverse Pickering emulsion. NIPAm monomers dissolving in suspended aqueous droplets were subsequently polymerized at different temperatures. The hollow microcapsules with SiO₂/PNIPAm nanocomposite shells were obtained when the reaction temperature was above the lower critical solution temperature (LCST) of PNIPAm. While the core-shell microcapsules with SiO₂ nanoparticles' shells and PNIPAm gel cores were produced when the polymerization was conducted at the temperature lower than LCST using UV light radiation. The supracolloidal structures with different cores could be tuned by simply changing reaction temperature, which was confirmed by confocal laser scanning microscopy and scanning electron microscopy. The interesting properties of both microcapsules were their ability of reversibly swelling during drying/wetting cycles and responsive to temperature stimulus. Such functional microcapsules may find applications in double control release system due to the presence of the supracolloidal structures and thermo-sensitivity.     

Preparation and characterization of crosslinked poly(methylmethacrylate) heat sensitive color-developing nanocapsules

The crosslinked poly(methylmethacrylate) (PMMA) heat sensitive color-developing nanocapsules were prepared by emulsion polymerization, in which leucocompound was used as a core material and methyl methacrylate and unsaturated hyperbranched poly(amide-ester) as wall-forming materials. The nanocapsules were characterized by Malvern particle size analysis, scanning electron microscopy, Fourier transform infrared spectrophotometry (FTIR), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), and densitometry. Triton X-100 was used as the emulsifier of emulsion polymerization. The effects of the emulsifier content on the particle size distribution and morphology of nanocapsules were discussed in detail. The FTIR analysis of leucocompound-containing nanocapsules demonstrated that leucocompound was successfully encapsulated in the crosslinked PMMA matrix. TGA results showed that the resultant nanocapsules had good thermal stabilities. The DSC analysis of the resultant nanocapsules indicated that the glass transition temperature of the nanocapsules was 117.9 °C. The resultant nanocapsules had narrower particle size distribution, smoother surface, and higher heat sensitive color-developing density with the percentage weight of emulsifier being 0.6 wt%.     

层层自主装法制备GO杂化多壁微胶囊及其稳定性的影响探究

氧化石墨烯(GO)纳米粒子片层结构可用作Pickering乳液分散剂,芯材离子液体的稳定分散是制备微胶囊的关键,以GO作为Pickering乳液分散剂,并设计以GO为单一壁材制备了自润滑微胶囊,考虑到GO具有优异的耐摩擦性能和良好的热稳定性,再通过层层自主装法,使得壁层之间可以通过静电吸附和氢键作用连接,从而合成多层GO壁自润滑微胶囊。重点研究pH值、油水比、GO的质量浓度对GO的Pickering乳液的影响及GO杂化多壁微胶囊制备的最佳稳定条件。实验证明在pH值为2,油水质量比为5%,GO质量浓度为0.1 mg/L的实验条件下制备的微胶囊最佳。     

Production of oil-containing crosslinked poly(vinyl alcohol) microcapsules by phase separation: Effect of process parameters on the capsule size distribution

Oil-containing poly(vinyl alcohol) (PVA) microcapsules in the size range of 5–20 μm were prepared by the simple coacervation of PVA followed by chemical crosslinking of the coacervated PVA membrane with glutaraldehyde. Coacervation of the aqueous polymer solution was achieved by the addition of a phase separation inducer (e.g., sodium sulfate). PVA of different grades (e.g., molecular weight and degree of hydrolysis) was utilized both as stabilizer and wall-forming material. Dispersion of the oil phase in the aqueous PVA solution was effected by a homogenizer. The effects of the various process parameters, such as the agitation speed, the type and concentration of PVA, the volume ratio of the internal oil phase to the external aqueous phase, the viscosity of the oil phase as well as the electrolyte concentration in the aqueous solution, on the stability and the size distribution of the emulsion droplets and microcapsules were experimentally investigated. It was shown that high agitation rates and low interfacial tension (e.g., high PVA concentrations) resulted in a significant reduction of the size of the emulsion droplets and microcapsules. On the other hand, as the viscosity and the amount of the dispersed oil phase increased, the capsule size increased. Finally, it was found that the concentration of the electrolyte significantly affected the stability of the (o/w) emulsion, the size and concentration of coacervated PVA colloidal aggregates, as well as the morphology of the polymer wall membrane formed by the adsorption of the polymer-rich phase to the oil/water interface. © 1996 John Wiley & Sons, Inc.     

Preparation of polyacrylate/paraffin microcapsules and its application in prolonged release of fragrance

The purpose of the present work was to develop a fragrance encapsulation system using polyacrylate/paraffin microcapsules. The Polyacrylate/paraffin microcapsules were fabricated by the method of suspension polymerization in Pickering emulsion. Morphology, size distribution, and thermal resistance of polyacrylate/paraffin microcapsules were investigated by scanning electron microscopy, light scattering particle size analyzer, and thermogravimetric analyzer. Results indicated that the crosslinked PMMA/paraffin microcapsules and P(MMA‐co‐BMA)/paraffin microcapsules prepared under optimal conditions presented regular spherical shape and similar size distribution. The crosslinked P(MMA‐co‐BMA)/paraffin microcapsules exhibited better thermal stability, with a thermal resistance temperature up to 184 °C. Fragrance microcapsules were prepared by encapsulating fragrance into crosslinked P(MMA‐co‐BMA)/paraffin microcapsules. The prolonged release performance of fragrance microcapsules was measured by ultraviolet‐visible near‐infrared spectrophotometer. 63.9% fragrance was retained after exposing fragrance microcapsules in air for 3 months, and the fragrance continued to release over 96 h in surfactant solution (sodium lauryl sulfonate, 20 wt %). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44136.     

Development of method for estimating drop diameter in the manufacturing process of functional O/W microcapsules

A new method for preparing functional O/W microcapsules using a process involving O/W/O emulsion as particle formation was developed. Coenzyme Q10 (CoQ10) or reduced coenzyme Q10 (QH) was used as the core substance. QH oxidized fast when exposed to air. O/W microcapsules were manufactured by conventional liquid phase drying method (LPD). The purpose of this study is to develop a simple method of estimating drop diameter which is possible to evaluate immediately the mean drop diameter during the microencapsulation process without the usual photographic measurement. This developed estimation is possible to predict a Sauter mean diameter by measuring the amount of inner CoQ10 released from O/W emulsion droplet. The amount of inner oil phase released from O/W emulsion has correlation with increased total surface area of O/W emulsion droplet caused by breaking droplet. Released rate of CoQ10 from O/W emulsion droplet to outer continuous phase under different rotational speed and emulsion viscosity was measured with an absorption spectrometer. As a result of the changes of released inner CoQ10 amount, droplet breakage under low emulsion viscosity was promoted by agitation speed. It is concluded that droplet dispersion state during manufacturing of O/W microcapsules was evaluated well by applying the developed estimation method.     

Preparation of acetamiprid-loaded polymeric microcapsules: Influence of preparation parameter in emulsion system on microcapsule characteristics

Microencapsulation of pesticides is a promising technique for avoiding high initial doses and multiple applications of the chemicals to agricultural land which cause environmental pollution. It is because the formulation is possible to improve the stability of the chemicals against environmental degradation and control the release rate. In the present study, polymeric microcapsules prepared by the solvent evaporation method via water-in-oil-in-water (W/O/W) emulsion were used as immobilization supports of acetamiprid, a water-soluble pesticide. The pesticide was loaded in the microcapsules by impregnating the polymeric supports with acetamiprid dissolved in an organic solvent. Increased volume ratio (ϕ) of inner aqueous phase to oil phase in the emulsion system contributed to more pores in the microcapsules and increase in the content of acetamiprid in the polymeric supports. Release rate of acetamiprid from the microcapsules could be controlled by changing ϕ.