溶剂蒸发法制备改性胺固化剂微胶囊的研究

以改性胺固化剂(1618)为囊芯、聚醚酰亚胺(PEI)为囊壁,采用溶剂蒸发法制备了EP(环氧树脂)固化用PEI包覆1618微胶囊。研究结果表明:固化剂芯材已被微胶囊PEI壁材成功包覆,其热稳定温度为130℃;以明胶作为分散剂时,制得的固化剂微胶囊表面光滑,分散性较好;随着芯壁比的增加,固化剂微胶囊的表面变得光滑、致密,并且其平均粒径减小(当芯壁比从1.0∶2.0增至1.5∶1.0时,平均粒径由45.8μm减至24.7μm)。     

同轴气喷法制备海藻酸钠-十六烷相变微胶囊

以海藻酸钠为壁材,十六烷为芯材,使用同轴气喷法制备相变微胶囊,考察了液体及气体流量对微胶囊粒径及壁厚的影响规律;采用光学显微镜、差示扫描量热(DSC)、热重分析(TG)等测试了微胶囊的平均粒径、包覆量、热稳定性及储热性能。结果表明同轴气喷法制备微胶囊的步骤简单,粒径的可控性较强。能够通过调节内、外管流量和气体流量控制微胶囊的粒径及壁厚。所制得的微胶囊粒径随液体流量减小而减小,随气体流量增大而减小。当海藻酸钠溶液流量为4 mL·h-1,十六烷的流量为2 mL·h-1,气体流量为25 L·h-1时,制得的相变微胶囊最小,其平均粒径约为90μm。相变微胶囊的囊芯包覆量随粒径的减小而减小,当微胶囊粒径约为300μm时,其包覆量达到90%以上。海藻酸钠囊壁对相变材料的储热性能不产生显著影响。     

石蜡-密胺树脂微胶囊相变材料制备与表征

研究中采用了正十八烷石蜡相变材料(PCM)芯材,密胺树脂作为囊壁材料,用原位聚合法制备成微胶囊材料。通过改变芯材和囊壁材料的质量比,探讨了微胶囊制备过程中O/W乳化液的相稳定性,并采用SEM,FT-IR,粒度分析仪和DSC对微胶囊的形态及性能进行表征。结果表明芯材增大O/W乳化液的相稳定性下降,微胶囊数量平均粒径和体积平均粒径均减小,当芯材和囊壁材料的质量比(Core/Shell)为1.5∶1时,微胶囊表面光滑致密,平均粒径为3.6μm,相变焓为98.6 MJ/mg。     

石蜡－密胺树脂微胶囊相变材料制备与表征

研究中采用了正十八烷石蜡相变材料（ PCM）芯材,密胺树脂作为囊壁材料,用原位聚合法制备成微胶囊材料。通过改变芯材和囊壁材料的质量比,探讨了微胶囊制备过程中O／W乳化液的相稳定性,并采用SEM, FT－IR,粒度分析仪和DSC对微胶囊的形态及性能进行表征。结果表明芯材增大O／W乳化液的相稳定性下降,微胶囊数量平均粒径和体积平均粒径均减小,当芯材和囊壁材料的质量比（ Core／Shell）为1．5：1时,微胶囊表面光滑致密,平均粒径为3．6μm,相变焓为98．6 MJ／mg。     

聚乳酸-石蜡微胶囊相变材料的制备及表征

制备了以聚乳酸(PLA)为壁材、石蜡为芯材的相变储能微胶囊。采用红外光谱、扫描电镜、热失重分析仪和差示扫描量热仪分析了微胶囊的结构及性能。结果表明:PLA已包覆到石蜡上,该微胶囊的粒径为5~10μm;微胶囊的热稳定性能在一定范围内得到了较大程度的提高,在300℃以下无质量损失;微胶囊的储热能力高达170.52 J/g。     

相变储能致密微胶囊的制备

分别采用界面聚合法、自由基聚合法首次制备了以聚脲为第一层壁材,以苯乙烯-二乙烯苯共聚物为第二层壁材,相变点16℃的石蜡为芯材的相变储热致密微胶囊.采用激光粒度分布仪、红外光谱分析仪.差示扫描量热分析仪、热重分析仪分析了制备的致密微胶囊的粒径分布、结构组成以及热性能.结果表明,相变储热致密微胶囊是复合相变材料,微胶囊的粒径均匀,热稳定性好,致密性优良不渗漏,其蓄热能力较好、可广泛应用于节能储能的目的.     

蜜胺树脂香精微胶囊的制备研究

为改进微胶囊化包覆效果、提高香精微胶囊的性能,通过对蜜胺树脂预聚过程中的三聚氰胺及甲醛摩尔比、pH值、反应温度及反应时间等因素进行研究,得到了用于香精微胶囊壁材的蜜胺树脂预聚体制备的最佳工艺:n(三聚氰胺)∶n(甲醛)=1∶3,反应温度70℃,pH=8~9的条件下反应15 min~25 min。采用该树脂预聚体以原位聚合法制备了香精微胶囊,所得微胶囊在显微镜观察下球形态良好,平均粒径较窄,约为1.5μm。FT-IR结果表明蜜胺树脂对香精的包覆良好;热失重分析说明了微胶囊大幅提高了香精的耐热性能。     

建筑用微胶囊型相变储热材料的制备及性能分析

为解决常规保温复合材料物理、化学性能不稳定的问题,提出了一种微胶囊包覆技术,将聚乙二醇复合芯材包覆于微胶囊中。以PEG 800和PEG 1000为主要材料,通过水浴加热法制备聚乙二醇复合芯材,在此基础上结合IPDI、DETA、SDBS等壁材制备微胶囊型相变储热材料。扫描电镜测试发现,微胶囊型相变储热材料对聚乙二醇复合芯材起到了良好的保护作用,且仍然保持了较为理想的储热性能,在建筑保温材料领域具有一定的应用价值。     

乙草胺蜜胺树脂微胶囊的制备与表征

[目的]制备具有缓释性能、环境友好型乙草胺剂型以丰富其剂型种类。[方法]以蜜胺树脂为囊壁、乙草胺为囊芯物质,通过原位聚法制备乙草胺蜜胺树脂微胶囊。利用傅里叶变换红外光谱仪、激光粒度仪、扫描电镜和紫外分光光度计对微胶囊表征。[结果]微胶囊粒径大小分布为0.5~10μm,表面光滑,包封率为86.91%,载药量为61.82%。     

应用于功能性热流体的相变微胶囊的制备与表征

相变材料微胶囊以其特有的蓄热性能在热能存储领域引起了人们的广泛关注。以异佛尔酮二异氰酸酯和四乙撑五胺为壁材原料,以相变点为20℃的石蜡为芯材,以非离子表面活性剂span60和tween60为乳化剂,利用界面聚合法制备了应用于功能热流体的相变微胶囊,分别用相差显微镜和差示扫描量热分析仪测定了微胶囊的形貌和热性能,结果表明所得微胶囊粒径分布均匀,其直径约为1.7μm。芯材含量约为92.4%,颗粒均匀,相变热124.47 J/g。相变微胶囊热稳定性高,具有好的致密性和不溶胀性。     

Preparation and characterization of double‐MF shell microPCMs used in building materials

A kind of double‐shell heat energy storage microcapsule was prepared used melamine formaldehyde (MF) resin as shell material, and the properties of the microcapsules were investigated. A phase change material, with melt point of 24°C and phase transition heat of 225.5J/g, was used as core. The microcapsules would be used in indoor walls to regulate the temperature and save energy. The surface morphological structure was examined by means of scanning electron microscopy. The strength of the shell was evaluated through observing the surface change after pressure by means of scanning electron microscopy. The average diameter of the microcapsules was 5 μm ～ 10 μm. Diameter of 1 μm ～ 5 μm could also be obtained by using different stirring speeds. The globular surface was smooth and compact. The thickness was 0.5 μm ～ 1 μm. Also, the melting point of the microcapsules was 24.7°C, nearly equal to the pure phase change material. The DSC results make clear that the polymer shell of the microcapsules does not influence the properties of the phase change material. It was also found that the avoiding penetration property of the double‐shell microcapsules was better than that of single shell, and the average diameter of 5 μm was better than 1 μm. With the increase of ratio of the core material, the compactability decreased, and the shell thickness decreased. The mass ratio of core and shell was 3 : 1 to ensure that the microcapsules had good heat storage function. The measuring test showed that the microcapsules did not rupture at a pressure of 1.96 × 10⁵ Pa. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1755–1762, 2005     

自修复微胶囊制备及微纳力学性能

采用一步原位聚合法制备了自修复微胶囊。应用光学显微镜、扫描电子显微镜和激光共聚焦显微镜对微胶囊壁厚、微结构进行了分析和表征。借助纳米探针对微胶囊及其壳材进行压痕实验测试其力学性能。结果表明,自修复微胶囊包裹完整,表面粗糙,微胶囊平均粒径为100μm,平均壁厚为10μm,微胶囊修复剂芯材含量约为75%;纳米压痕分析显示微胶囊的弹性模量比环氧树脂的略小,说明了当环氧树脂基体内裂纹扩展时,裂纹更易于向微胶囊扩展,证明了环氧树脂微裂纹打开微胶囊释放修复剂的可行性。     

Synthesis and characterization of chitosan/urea‐formaldehyde shell microcapsules containing dicyclopentadiene

Microcapsules containing healing agent have been used to develop the self‐healing composites. These microcapsules must possess special properties during the use of composites such as stability in surrounding, appropriate mechanical strength, and lower permeability. A new series of microcapsules containing dicyclopentadiene with chitosan/urea‐formaldehyde copolymer as shell materials were synthesized by in situ copolymerization technology. The microencapsulating mechanism was discussed and the process was explained. Also, the factors influencing the preparation of microcapsules were analyzed. The morphology and shell wall thickness of microcapsules were observed by using scanning electron microscopy. The size of microcapsules was measured using optical microscope and the size distribution was investigated based on data sets of at least 200 measurements. The chemical structure and thermal properties of microcapsules were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis, respectively. The storage stability and isothermal aging experiment of microcapsules were also investigated. Results indicted that the chitosan/urea‐formaldehyde microcapsules containing dicyclopentadiene were synthesized successfully; the copolymerization occurred between chitosan and urea‐formaldehyde prepolymer. The microcapsule size is in the range of 10–160 μm with an average of 45 μm. The shell thickness of microcapsules is in the range of 1–7 μm and the core content of microcapsules is 67%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microcapsules prepared from a polycondensate‐based cement dispersant via layer‐by‐layer self‐assembly on melamine‐formaldehyde core templates

Novel microcapsules were prepared from colloidal core–shell particles by acid dissolution of the organic core. Weakly crosslinked, monodisperse and spherical melamine‐formaldehyde polycondensate particles (diameter ～ 1 μm) were synthesized as core template and coated with multilayers of an anionic polyelectrolyte via layer‐by‐layer deposition technique. As polyelectrolytes, an anionic naphthalenesulfonate formaldehyde polycondensate that is a common concrete superplasticizer and thus industrially available, and cationic poly(allylamine hydrochloride) were used. Core removal was achieved by soaking the core–shell particles in aqueous hydrochloric acid at pH 1.6, resulting in hollow microcapsules consisting of the polyelectrolytes. Characterization of the template, the core–shell particles, and the microcapsules plus tracking of the layer‐by‐layer polyelectrolyte deposition was performed by means of zeta potential measurement and scanning electron microscopy. The microcapsules might be useful as microcontainers for cement additives. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

纳米 SiO2改性石蜡相变微胶囊涂料的制备及性能表征

相变微胶囊在能源节约方面可以起到重要作用。以石蜡为芯材,三聚氰胺树脂为壳材,并使用纳米 SiO2作为改性剂,采用原位聚合法制备相变微胶囊。研究了纳米 SiO2用量对微胶囊性能的影响。通过差示扫描量热仪（ DSC）、扫描电子显微镜（ SEM）以及同步热分析仪（ TGA）等对相变微胶囊的相变特性、表面形貌、热稳定性以及包裹率等进行了测试表征。结果表明：纳米 SiO2用量为 5%的改性相变微胶囊有最大的相变潜热和包裹率,分别为 145. 7 kJ/kg和 81. 8%,微胶囊的相变温度为 29. 1 ℃,粒径约 60 μm。将改性相变微胶囊作为添加剂加入涂料中,随着添加量的增加,复合涂料的储放热性能依次增强。相变微胶囊用量为 30%的复合涂料与未添加微胶囊的涂料相比较,当温度从 15 ℃左右升温至 31 ℃所需时间增加了 12 min左右,温度从 38 ℃左右降温至 20 ℃所需时间增加了 6 min左右。     

Preparation and properties of phase‐change heat‐storage UV curable polyurethane acrylate coating

Phase‐change heat‐storage UV curable polyurethane acrylate (PUA) coating was prepared by applying microencapsulated phase change materials (microPCMs) to PUA coating. MicroPCMs containing paraffin core with melamine‐formaldehyde shell were synthesized by in situ polymerization. The effect of stirring speed, emulsification time, emulsifier amount, and core/shell mass ratio on particle size, morphology, and phase change properties of the microPCMs was studied by using laser particle size analyzer, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopic analysis, scanning electron microscopy, and differential scanning calorimetry. The results showed that the diameter of the microcapsules decreased with the increase of stirring speed, emulsification time, and emulsifier amount. When the mass ratio of emulsifier to paraffin is 6%, microcapsules fabricated with a core/shell ratio of 75/25 have a compact surface and a mean particle size of 30 μm. The sample made under the above conditions has a higher efficiency of microencapsulation than other samples and was applied to PUA coating. The dispersion of microPCMs in coating and heat‐storage properties of the coating were investigated. The results illustrated that the phase‐change heat‐storage UV curable PUA coating can store energy and insulate heat. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41266.     

Preparation and characterization of poly(urea-formaldehyde) microcapsules filled with epoxy resins

The preparation of microcapsules applied to the fabrication of self-healing composites has been paid more attentions. A new series of microcapsules were prepared by in situ polymerization technology with poly(urea-formaldehyde) (PUF) as a shell material and a mixture of epoxy resins (diglycidyl ether of bisphenol A: DGEBPA) and 1-butyl glycidyl ether (BGE) as core materials. The microencapsulating process of core material was monitored using optical microscopy (OM). The chemical structure of microcapsule was characterized using Fourier-transform infrared spectroscopy (FTIR). Morphology and shell wall thickness of microcapsule were observed using metalloscope (MS), scanning electron microscopy (SEM) and OM, respectively. The effects of different pre-polymers, weight ratios of urea to formaldehyde (U-F) and the agitation rates on the physical properties of microcapsules were investigated. The storage stability of microcapsules at different times and temperatures was analyzed. The thermal properties of microcapsules were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results indicate that PUF microcapsules containing epoxy resins can be synthesized successfully, and during the microencapsulation, the epoxide rings in epoxy resins are hardly affected by the surrounding media. The rough outer surface of microcapsule is composed of agglomerated PUF nanoparticles. The size and surface morphology of microcapsule can be controlled by selecting different processing parameters. The microcapsules basically exhibit good storage stability at room temperature, and they are chemically stable before the heating temperature is up to approximately 238 °C.     

石蜡微胶囊的溶胶-凝胶法改性

以脲醛树脂为囊壁,氯化铵为固化剂,采用原位聚合法包覆石蜡合成相变储能微胶囊,使用溶胶-凝胶法对微胶囊进行表面改性,并用硅烷偶联剂改性复合SiO2溶胶。采用傅里叶红外光谱仪、差示扫描量热仪和扫描电子显微镜分析了微胶囊的化学结构、储热性能和微胶囊改性前后的表观形貌及分散状态,并运用高度法测试了改性微胶囊的亲水性。研究表明,通过溶胶-凝胶法与硅烷偶联剂改性相结合,可提高微胶囊的亲水性、无机相容性和致密性,并改善复合微胶囊粒子的分散程度。     

醇酸树脂微胶囊的制备及环氧涂层自修复性能

采用三聚氰胺-脲醛树脂（MUF）为壁材、合成的花椒籽油醇酸树脂为芯材，原位聚合法制备自修复微胶囊，探讨了微胶囊的制备工艺。并采用扫描电子显微镜（SEM）、红外光谱仪（FTIR）、热重分析仪（TGA）和粒径分析仪对微胶囊的表面形貌、化学结构、热稳定性及其粒径分布进行了测试表征。将醇酸树脂微胶囊分散到环氧基体中，研究了环氧涂层的力学性能和自修复性能。实验结果表明，当乳化剂浓度为2.0g/L、芯壁比为2∶1、终点pH为3.5时，微胶囊呈球形结构，无明显的缺陷和损伤，平均粒径为97.44μm，热稳定性良好。当添加质量分数5%的微胶囊时，与未添加微胶囊的自修复涂层相比，其弯曲强度、拉伸强度、黏结强度及其冲击强度分别提高了50.4%、50.0%、40.0%及25.2%，且涂层的自修复性能良好。     

Influence of microcapsule shell material on the mechanical behavior of epoxy composites for self‐healing applications

In this article, we have studied the effect of microcapsule shell material on the mechanical behavior of self‐healing epoxy composites. Liquid epoxy healant was encapsulated in melamine‐formaldehyde (MF) and urea‐formaldehyde (UF), using emulsion polymerization technique to prepare microcapsules of different shell walls. The core content of the microcapsules, as determined by solvent extraction technique was found to be 65 ± 4%, irrespective of the shell wall of microcapsule. Morphological investigations reveal a rough texture of the spherical microcapsules, which was attributed to the presence of protruding polymer nanoparticles on the surface. Epoxy composites containing UF and MF microcapsules (3–15% w/w) were prepared by room temperature curing and their mechanical behaviour was studied under both quasi‐static and dynamic loadings. The tensile strength, modulus, and impact resistance of the matrix was found to decrease with increasing amount of microcapsule in the formulation, irrespective of the shell wall material used for encapsulation. Interestingly, substantial improvement in the fracture toughness of the base resin was observed. Morphological investigations on the cracked surface revealed features like crack pinning, crack bowing, microcracking and crack path deflection, which were used to explain the toughened nature of microcapsule containing epoxy composites. Our studies clearly indicate that the microcapsule shell wall material does not play any significant role in defining the mechanical properties of the composites. In addition, presence of secondary amine functionalities in UF and MF shell wall do not interfere with the reaction of epoxy with triethylene tetramine hardener during the curing process. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40572.