细粒径石蜡微胶囊相变材料的制备与性能

采用阳离子和非离子复配乳化剂,通过原位聚合制备以丙烯酸酯为壁材,石蜡为芯材的细粒径微胶囊相变材料.采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、差示扫描量热(DSC)、热重(TG)及激光粒度仪分析表征了微胶囊相变材料的化学结构、表面形貌和热性能.结果表明,乳化剂的种类和壁材单体的配比对微胶囊性能有重要的影响.当采用阳离子和非离子复配乳化剂,壁材中单体甲基丙烯酸甲酯(MMA)与丙烯酸(AA)的质量比为9∶1时,微胶囊相变材料呈球形且表面光滑紧凑,尺寸仅为0.2~0.35μm,具有良好的储热能力,相变潜热高达169 J/g;微胶囊中壁材对石蜡芯材的分解具有明显热阻滞作用,分解温度比纯石蜡提高了150℃.     

纳米二氧化硅改性石蜡微胶囊相变储能材料的研究

以石蜡为芯材,甲基丙烯酸甲酯-丙烯酸共聚物为壁材,纳米SiO2为改性剂,采用原位聚合法制备了石蜡微胶囊相变储能材料,系统研究了添加纳米SiO2对石蜡微胶囊相变材料性能的影响;采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、示差扫描量热法(DSC)和热重分析(TGA)等对石蜡微胶囊相变材料的化学结构、表面形貌和热性能进行了表征.研究表明,纳米SiO2能够有效提高微胶囊壁材的热稳定性,当丙烯酸酯壁材中添加3％改性纳米SiO2时,微胶囊呈球形且表面光滑,尺寸250 ～ 300 nm,具有良好的储热能力,相变潜热高达134.79 J/g,分解温度比未添加改性纳米SiO2的石蜡微胶囊提高了40 K,经过1000次热循环测试,石蜡渗漏率仅2.96％.     

十八烷/聚(St-MMA)相变微胶囊制备及表征

采用乳液聚合的方法,分别选取聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)或苯乙烯和甲基丙烯酸甲酯的共聚物为壁材,正十八烷为芯材,十二烷基苯磺酸钠(SDBS)为乳化剂,制作相变储能微胶囊。用粒径分析仪、透射电子显微镜(TEM)、热重分析仪(TG)和示差扫描量热测试仪(DSC)对微胶囊的形貌、相变热性能和热稳定性分别进行表征。结果表明:壁材选取两者共聚物,当两种单体的比例为St∶MMA=1∶5,SDBS用量为1.5g(总质量的3%)时,微胶囊粒径大小均匀,粒子分散性好,壁材的包裹性好。微胶囊的放热峰为起始温度为27.3℃,终止温度为31.9℃,相变温度为28.9℃,相变焓为48.4J/g。TG表明长期使用温度不能超过131℃。IR分析微胶囊中含有芯材和壁材。这种十八烷/聚(St-MMA)相变微胶囊可以用于诸能材料。     

界面聚合法制备正二十烷微胶囊化相变储热材料

用界面聚合的方法,以甲苯-2,4-二异氰酸酯(TDI)和己二胺(HDA)为反应单体,非离子表面活性剂聚乙二醇壬基苯基醚(OP)为乳化剂,合成了正二十烷为相变材料的聚脲包覆微胶囊. 结果表明,二异氰酸酯和己二胺按质量比为1.5∶ 0.8进行反应. 空心微胶囊的直径约为0.2 μm,含正二十烷微胶囊直径为2~6 μm. 红外光谱分析证明, 囊壁聚脲是由TDI及HDA 2种单体形成. 正二十烷包裹效率为65%~80%. 微胶囊的熔点接近囊芯正二十烷的熔点,而其储热量在壁材固定时随囊芯的量而变. 热重分析结果表明,囊芯正二十烷、含正二十烷的微胶囊以及壁材聚脲,能够耐受的温度分别约为130、165及250 ℃.     

高芯材含量聚苯乙烯石蜡微胶囊的制备及性能研究

为解决石蜡在使用过程中的一系列问题,以聚苯乙烯为壁材,58~#石蜡为芯材,采用悬浮聚合法制备了高芯材含量的微胶囊.考察了二己烯基苯(DVB)用量、芯壁比、复合改性时共聚单体种类和用量对微胶囊的影响.采用FT-IR、SEM、DSC、TG表征了微胶囊的结构、形貌、储热性能及热稳定性能.实验结果表明,DVB用量11%、芯壁比3∶1制备的微胶囊大小均匀,无团聚现象;交联改性的同时,加入20%MA单体共聚改性制备的微胶囊形貌好,热稳定性最佳,微胶囊中石蜡含量为91.7%时储热性能最优.     

一种致密的相变储能微胶囊的制备与表征

制备了以聚脲为第一壁材、苯乙烯-二乙烯苯为第二壁材,以相变点在16℃左右的石蜡为芯材的相变储能微胶囊。采用红外光谱、差示扫描量热分析、热重分析测试技术表征了制备的相变储能微胶囊的结构组成以及热性能;采用溶剂淋洗法研究了影响包覆率的因素。结果表明,相变储热微胶囊是复合相变材料,微胶囊的热稳定性好,致密性优良;通过对水油比、乳化剂及苯乙烯-二乙烯苯用量等各因素对微胶囊包覆率影响的讨论,得出在水与油质量比3.2,乳化剂相对于水的质量分数为2%时,加入苯乙烯与二乙烯苯质量比为10∶1混合液的质量分数为6.0%时,其包覆率达81.14%;制备的微胶囊能耐较高温度,在150℃以下无质量损失,且微胶囊储热能力高达80J/g。同时发现,储热能力与芯壁比有关,比值越大储热潜能越高。     

界面聚合法制备正二十烷微胶囊化相变储热材料

采用界面聚合的方法, 以甲苯鄄2,4-二异氰酸酯(TDI)和乙二胺(EDA)为反应单体, 非离子表面活性剂聚乙二醇壬基苯基醚(OP)为乳化剂, 合成了正二十烷为相变材料的聚脲包覆微胶囊. 结果表明, 二异氰酸酯和乙二胺按质量比1.9:1 进行反应. 以透射电镜和激光粒度分析仪分析微胶囊, 测得空心微胶囊直径约为0.2 μm, 含正二十烷微胶囊约为2-6 μm. 红外光谱分析证明, 壁材料聚脲是由TDI 及EDA 两种单体形成的. 正二十烷的包裹效率约为75%. 微胶囊的熔点接近囊芯二十烷的熔点, 而其储热量在壁材固定时随囊芯的量而变. 热重分析表明, 囊芯正二十烷、含正二十烷的微胶囊以及壁材料聚脲, 能够耐受的温度分别约为130 ℃、170 ℃及270 ℃.     

聚二甲基丙烯酸乙二醇酯壁材微胶囊的制备及其表征

采用界面自由基聚合的方法,制备了以聚二甲基丙烯酸乙二醇酯(PEGDMA)为壁材,薄荷素油(DPO)与石蜡或者三辛癸酸甘油酯(GTCC)的混合物为芯材的微胶囊.微胶囊壁材是二甲基丙烯酸乙二醇酯(EGDMA)单体通过界面自由基聚合形成的高聚物PEGDMA.提出了该界面自由基聚合形成PEGDMA的机理过程.利用光学显微镜和扫描电镜探究了乳化剂类型、芯材组成和固化温度对微胶囊形貌的影响.用傅里叶红外光谱对微胶囊的化学结构进行了表征.利用紫外分光光度计测出了未被微胶囊包埋的芯材占总芯材的百分比(free oil).并用热重分析仪分析了微胶囊的热稳定性能,讨论了固化时间对微胶囊热性能的影响.结果表明,采用阿拉伯树胶为乳化剂,芯材组成为质量比M_(DPO)/M_(GTCC)=1∶1,在60℃下固化1 h,制备出的微胶囊为饱满的球形状,表面光滑.同时测得该体系中芯材的free oil为26.5 wt%.PEGDMA微胶囊在60℃固化温度下反应3 h,具有很好热稳定性,且固化温度升高能提高微胶囊的热稳定性.所制备的微胶囊无毒,在个人护理品和医药领域具有广泛的应用前景.     

以聚脲为囊壁薄荷素油微胶囊的制备及表征

采用界面聚合法,以薄荷素油为芯材,以异佛尔酮二异氰酸酯为壁材单体,在催化剂四甲基乙二胺作用下和水反应形成聚脲外壳,制备出了薄荷素油微胶囊.通过扫描电镜、激光粒度分析仪、傅里叶红外光谱仪及热重分析仪分别对香精微胶囊的表面形貌、粒径分布、单体反应情况和热稳定性进行了分析表征.通过紫外可见分光光度计对香精微胶囊包覆率进行了测定.并分析了均质化速率和微胶囊平均粒径的关系以及不同乳化剂种类和芯壁比条件下微胶囊的形貌特征.结果表明,微胶囊平均粒径随均质化速率的增大而减小,下降到1μm左右时趋于平稳,当乳化剂采用聚乙烯醇且芯壁比为4∶1时,微胶囊形貌最佳,为规整球形.最终测得微胶囊芯材包覆率为84.09 wt%,粉末状微胶囊样品含油率为72.64 wt%,并且微胶囊芯材具有良好的热稳定性.     

三聚氰胺-甲醛树脂包裹环氧树脂微胶囊的制备及表征

针对环氧树脂基材料的自修复,选取四氢邻苯二甲酸二缩水甘油酯作为芯材,采用三聚氰胺-甲醛树脂为壁材,对其进行微胶囊化包裹.结果表明,制得的具有单囊结构的环氧树脂微胶囊,胶囊粒径较小(约6.7μm)、囊壁较薄(约0.2μm)、芯含量较高(83.2 wt%),囊壁内、外表面光滑致密,胶囊具有良好的密闭性和耐热性;在微胶囊化过程中,三聚氰胺-甲醛树脂的缩聚反应动力学起关键作用,芯材没有参与囊壁形成的交联反应;包裹后的芯材活性保持不变,胶囊被复合到材料过程中囊芯活性也保持不变;胶囊的强度较高,能承受与基体材料复合过程中的外力作用,且与基体材料间粘结良好,在裂纹形成过程中能够随基体同时开裂.     

包含聚苯胺的相变材料纳胶囊的制备及其性能

采用自由基乳液聚合法和原位聚合法制备了包含聚苯胺均匀分散在正十八烷中的悬浮体系的交联聚甲基丙烯酸甲酯为囊壁的相变材料纳胶囊(NanoPCMs). 采用扫描电子显微镜(SEM)、差示扫描量热仪(DSC)、热重分析仪(TG)和广角X射线衍射仪(WAXD)等手段分别考察了成核剂聚苯胺的添加量对相变材料纳胶囊表面形态、结晶性能、热稳定性及结晶行为等的影响. 实验结果表明：包含有聚苯胺的相变材料纳胶囊,成核剂的存在对其形貌、粒径、包覆率和结晶行为影响较小,耐热性略有所降低,添加1.5 g 苯胺时生成的成核剂聚苯胺可以有效改善其过冷结晶行为.     

Structure and thermal stability of microencapsulated phase-change materials

A series of microcapsules containing n-octadecane with a urea-melamine-formaldehyde copolymer shell were synthesized by in-situ polymerization. The surface morphology, diameter, melting and crystallization properties, and thermal stability of the microcapsules were investigated by using FTIR, SEM, DSC, TGA and DTA. The diameters of the microcapsules are in the range of 0.2–5.6 m. The n-octadecane contents in the microcapsules are in the range of 65–78wt%. The mole ratio of urea-melamine has been found to have no effect on the melting temperature of the microcapsules. Two crystallization peaks on the DSC cooling curve have been observed. The thermal damage mechanisms are the liquefied n-octadecane leaking from the microcapsule and breakage of the shell due to the mismatch of thermal expansion of the core and shell materials at high temperatures. The thermal stability of materials can be enhanced up to 10 °C by the copolymerization of urea, melamine and formaldehyde in a mole ratio 0.2:0.8:3. The thermal stability of 160 °C heat-treated microcapsules containing 8.8% cyclohexane can be further enhanced up to approximately 37 °C.     

Preparation of PCM microcapsules by complex coacervation of silk fibroin and chitosan

Phase change material microcapsules were prepared by complex coacervation of silk fibroin (SF) and chitosan (CHI). n-Eicosane was used as the core material. The effects of SF/CHI ratio, and percentage of cross-linking agent and n-Eicosane content on the properties of microcapsules were studied. The size distribution and the surface morphology of microcapsules were characterized by optical and scanning electron microscopy. The encapsulation of core material was determined by energy dispersive spectrometer analysis. The results indicated that SF/CHI microcapsules were prepared successfully. Microcapsules had smooth outer surface when the ratio of SF to CHI was close to 5. On the other hand, at high SF/CHI ratios (≥14), microcapsules showed a two-layer structure, an inner compact layer, and an outer, more porous, sponge-like layer. The highest microencapsulation efficiency was obtained at a SF/CHI ratio of 20 in the presence of 0.9% cross-linking agent and of 1.5% n-Eicosane content.     

Novel polyphenylene oxide microcapsules filled with epoxy resins

Novel polyphenylene oxide (PPO) microcapsules filled with epoxy resins (PPOMCs) were synthesized by in situ polymerization technology with 2, 6‐dimethy phenol as shell materials and diglycidyl ether of bisphenol A epoxy resins as core materials. The structures and morphologies of PPOMCs were characterized using Fourier‐transform infrared spectroscopy, micro‐confocal Raman microscope, laser scanning confocal microscopy, scanning electron microscopy and optical microscopy, respectively. The thermal properties of PPOMCs were investigated using differential scanning calorimetry and thermogravimetric analysis. The influences of different processing parameters such as the weight ratio of shell material to core material, kind of surfactant and reaction temperature on the morphologies and sizes of PPOMCs were investigated. Preliminary investigation on application of PPOMCs to thermosetting resins 4,4′‐bismaleimidodiphenylmethane/O,O′‐diallylbisphenol A (BMI/BA) system was conducted. Results indicate that PPOMCs can be synthesized successfully. The sizes and surface morphologies of PPOMCs may be significantly affected by different processing parameters. PPOMCs can be well prepared at about 30°C, and they depend strongly on the kind of surfactant and the weight ratio of shell material to core material. PPOMCs basically exhibit high thermal stability when the temperature is below 258°C. The addition of PPOMCs can improve the mechanical properties and maintain the thermal properties of BMI/BA system. The released core materials from PPOMCs may repair the matrix cracks through the polymerization of epoxy resins initiated by curing agent. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of cationic core-shell latex particles

Surfactant-free seeded (core-shell) polymerization of cationic polymer colloids is presented. Polystyrene core particles with sizes between 200 nm and 500 nm were synthesized. The number average diameter of the colloidal core particles increased with increasing monomer concentration. Cationic shells were introduced by co-polymerizing styrene with the cationic monomers (vinylbenzyl)trimethylammonium chloride (VBTMAC), [(2-methacryloyloxy)ethyl] trimethylammonium chloride (METMAC) and [(2-(acryloyloxy)ethyl] trimethylammonium chloride (AETMAC) onto the polystyrene cores. The cationic monomer AETMAC, undocumented to our knowledge in colloid synthesis, produced the best cationic shells and could be incorporated at much higher concentrations in the shell compared to the commonly used VBTMAC and METMAC, which yielded undesired polyelectrolyte side products already at relatively low cationic monomer concentrations. In shell formation, feed concentrations of AETMAC between 1.3 mol% (2.4 wt%) and 10.7 mol% (20 wt%) in styrene could be employed, allowing us to control colloid surface charge density over a wide range. The influence of various polymerization parameters (initiator concentration, cross-linking agent, and ionic strength) on the co-polymerization process with AETMAC is discussed. Core-shell particles were characterized using HR-SEM, potentiometric titration and zeta potential measurements.     

Core–shell and gradient morphology polymer particles analyzed by X‐ray photoelectron spectroscopy: Effect of monomer feed order

The synthesis of composite latex particles possessing core–shell and gradient morphologies, respectively, using seeded starve‐fed semibatch emulsion polymerization of styrene (St) and methyl methacrylate (MMA) is presented. The focus is on the effect of the monomer feed order on the particle morphology development. The particle morphology is assessed using a novel approach which entails comparing the experimental surface composition as a function of polymerization time (particle growth) obtained by X‐ray photoelectron spectroscopy with the predicted surface composition using a mass balance mathematical model. Both types of composite latexes (core–shell and gradient) feature changes with polymerization time in the oxygen/carbon surface composition which enables one to track the morphology development. Differential scanning calorimetry is also implemented to analyze the extent of phase separation. The monomer feed order is shown to play a crucial role—under the present conditions, gradient and core–shell particles are obtained if the feed order is St/MMA (St fed first), but not if the feed order is reversed. These findings illustrate that thermodynamic factors are important, given that thermodynamically it is more favorable for MMA‐rich chains to occupy the oil–water interface to reduce the interfacial tension. Systems where St is the second stage monomer lead to mixed structures rather than the targeted core–shell or gradient morphology with St‐rich chains at the particle surface. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2513–2526     

Microgels containing methacrylic acid: effects of composition on pH-triggered swelling and gelation behaviours

pH-responsive microgels are cross-linked polymer colloids that swell when the pH approaches the pK _a of the particles. In this work, we present a comprehensive investigation of pH-triggered particle swelling and gel formation for a range of microgels containing methacrylic acid (MAA). The microgels investigated have the general composition poly(A/MAA/X), where A and X are the primary co-monomer and cross-linking monomer, respectively. The primary co-monomers were methyl methacrylate (MMA), ethyl acrylate (EA) or butyl methacrylate. The cross-linking monomers were either butanediol diacrylate (BDDA) or ethyleneglycol dimethacrylate (EGDMA). The microgels were studied using scanning electron microscopy, photon correlation spectroscopy (PCS) and dynamic rheology measurements. Gel phase diagrams were also constructed. The particles swelled significantly at pH values greater than approximately 6.0. It was shown that poly(EA/MAA/X) microgels swelled more strongly than poly(MMA/MAA/X) microgels. Furthermore, greater swelling occurred for particles prepared using EGDMA than BDDA. Concentrated dispersions of all the microgels studied exhibited pH-triggered gel formation. It was found that the fluid-to-gel transitions for the majority of the six microgel dispersions investigated could be explained using PCS data. In those cases, gelation was attributed to a colloidal glass transition. Interestingly, the microgels that were considered to have the highest hydrophobic content gelation occurred under conditions where little particle swelling was evident from PCS. The data presented show that gelled poly(EA/MAA/BDDA) and poly(MMA/MAA/EGDMA) microgel dispersions have the strongest elasticities at pH = 7.     

Synthesis and surface properties of self-crosslinking core–shell acrylic copolymer emulsions containing fluorine/silicone in the shell

Stable emulsions of a core–shell acrylic copolymer (non-crosslinkable V0, and crosslinkable V2, V4, V6, and V8, where the numbers indicate the wt% of crosslinking agent based on the total acrylate monomer content) containing butyl acrylate (BA, 45 wt%), glycidyl methacrylate (GMA, 45 wt%), heptadecafluorodecyl methacrylate (PFA, 10 wt%), and various contents of crosslinking agent (vinyltriethoxysilane, VTES) were synthesized using a three-stage seeded emulsion polymerization process with a small amount of surfactant. The average particle size and viscosity of emulsions increased significantly with increasing VTES content. This study examined the effects of the VTES content on the surface/mechanical properties of self-crosslinked copolymer film samples containing a fixed acrylate monomer content to find the optimum VTES content. XPS showed that the film–air surface of the copolymer samples had a higher fluorine/silicone content than the film–dish interface. The tensile strength/modulus, thermal stability, and two Tgs (α and β Tgs) of the film samples increased significantly with increasing VTES content. The contact angle of the film samples increased with increasing VTES content up to approximately 6 wt%, and then decreased slightly. The optimum VTES content was approximately 6 wt% based on the total acrylate monomer content to obtain a high water/oil repellent coating material (V6) with the highest water/methylene iodide-contact angles (118.2°/81.8°) and lowest surface energy (18.4 mN/m).     

微波辅助核-壳型Cr(Ⅲ)离子印迹聚合物的制备及在尿液中的分离应用

以3-氨丙基三甲氧基硅烷为离子配体,正硅酸乙酯为交联剂,借助微波辅助加热,在二氧化硅表面快速制备Cr(Ⅲ)离子印迹聚合物,聚合时间比常规时间缩短了5倍.利用扫描电镜对印迹聚合物形貌进行了表征,结果表明,该印迹聚合物粒径分布均匀,Cr(Ⅲ)离子成功地包覆在厚度约为40nm的印迹壳层内.详细地探讨了该印迹材料的吸附性能,并利用该印迹聚合物作为固相萃取填充料,成功地用于尿样中Cr(Ⅲ)的固相萃取.