丙烯酸共聚物囊壁的正十八烷微胶囊的制备和性能表征

以二丙烯酸1,4-丁二醇酯为交联剂, 成功制备了甲基丙烯酸甲酯-甲基丙烯酸共聚物为壁材, 正十八烷为囊芯的相变材料微胶囊. 采用扫描电子显微镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TG)分别考察了单体与芯材投料比、单体浓度和交联剂的含量对微胶囊形貌、相变热性能、热稳定性能的影响. 实验结果表明: 随着单体与芯材投料比或单体浓度的增加, 微胶囊表面均变得致密, 壁厚增加; 随着交联剂含量的增加, 微胶囊的表面变得更加致密光滑, 热稳定性显著增强; 随着单体与芯材投料比的增大, 微胶囊热焓值减小, 被包裹的囊芯含量减少.     

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℃.     

石墨烯/正十八烷微胶囊的制备与及其热性能研究

以石墨烯/正十八烷为芯材,三聚氰胺-尿素-甲醛树脂(MUF)为壁材,苯乙烯马来酸酐共聚物(SMA)为乳化剂,采用乳液聚合法制备相变微胶囊.系统研究了石墨烯对于正十八烷微胶囊性能的影响.采用场发射扫描电子显微镜(FE-SEM)、傅里叶变换红外光谱分析仪(FTIR)、拉曼光谱仪、X射线衍射仪(XRD)、Hot Disk热常数分析仪、示差扫描量热仪(DSC)和热重分析仪(TGA)对相变微胶囊的外貌形态、晶型结构和热性能进行表征和分析.结果表明,微胶囊呈圆球形且光滑,粒径约为1~30μm.当石墨烯添加量为0.1 g时,微胶囊的形貌无明显变化.当加入过量石墨烯时,微胶囊出现了明显的团聚现象.XRD测试表明,包覆于微胶囊中的石墨烯没有使微胶囊的结晶峰位置发生明显的偏移,这对于微胶囊的实际应用是有利的.微胶囊的相变热焓和包覆率随着石墨烯的加入而不断减小,但芯材的过冷现象得到了明显的改善.石墨烯对于微胶囊传热性能的提升有着显著的效果.当石墨烯的添加量为0.2 g时,微胶囊的导热系数为0.092 W·m-1·K-1,与纯微胶囊相比提高了约51%,这说明石墨烯改善了传统相变微胶囊的传热性能,提升了相变微胶囊的应用性能.     

石蜡/P(MMA-co-AA)核壳结构相变蓄能微胶囊的制备

以熔点在58~60℃的半精炼石蜡作为相变芯材,与单体、分散剂水溶液形成核壳结构分散液,室温下自由基聚合制备甲基丙烯酸甲酯-丙烯酸的共聚物(P(MMA-co-AA))为壳材的微胶囊.分别用相差显微镜、扫描电镜、差示扫描量热分析仪和傅里叶变换红外光谱仪测定了微胶囊的形貌、热性能和壳材化学结构.微胶囊的直径范围为1~5μm,其中相变芯材的含量可达70%左右,具有较高的相变潜热(99 J/g),有望应用于空调、供暖等领域.     

具有薄荷香味的相变微胶囊的制备与表征

利用界面聚合法,以异佛尔酮二异氰酸酯与己二胺为单体聚合形成的聚脲为外壳,以正十八烷、薄荷素油的混合物为芯材,制备了具有薄荷香味的相变微胶囊。利用光学显微镜、扫描电镜、红外光谱仪、差示扫描量热仪、热重分析仪等对微胶囊的形貌、化学结构和热性能进行了表征。结果表明:制备的微胶囊为球形,平均粒径约7.0μm,有较高的储热能力和较好的热稳定性;芯材中添加8.3%的正十四醇或高熔点石蜡,可很好地抑制相变微胶囊的过冷现象。     

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％.     

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 ℃.     

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 ℃.     

硅橡胶包覆十八烷/聚(St-MMA)储能微胶囊复合材料制备及热性能

以十八烷/聚(苯乙烯-甲基丙烯酸甲酯)(P(St-MMA))微胶囊为相变材料,硅橡胶作为载体,制备了十八烷/P(St-MMA)/硅橡胶复合材料。研究了微胶囊的加入方式及加入量,硅橡胶包覆方法。通过红外光谱(IR)和扫描电镜(SEM)研究复合材料的结构和形貌。通过力学性能测试如拉伸强度、扯断伸长率,确定最佳的加工方法。通过热重分析法(TG)、差示扫描量热法(DSC)和储热性能对复合材料的热性能进行研究。结果表明,十八烷制成微胶囊加入到硅橡胶中,且微胶囊加入量是2份时,十八烷/P(St-MMA)微胶囊/硅橡胶的热稳定性热稳定性及力学性能较好。室温硅橡胶包覆微胶囊掺混固化法制备的复合材料的力学性能优于直接共混后热固化法和混炼涂抹后热固化法。十八烷/P(MMA-St)/硅橡胶复合材料的焓值为67.6J/g,储能效果好。     

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.     

A novel method for encapsulation of a liquid crystal in monodisperse micron-sized polymer particles

Liquid crystals (LCs) encapsulated in monodisperse micron-sized polymer particles were prepared to control the size and size distribution of LC droplets in polymer-dispersed LCs. The poly(methyl methacrylate) (PMMA) seed particles were swollen with the mixture of liquid crystal, monomers (methyl methacrylate and styrene) and initiator by using a diffusion-controlled swelling method. A single LC domain was produced by the phase separation between PMMA and LC through polymerization. The optical microscopy and scanning electron microscopy showed that the particles are highly monodisperse with core–shell structure. Moreover, monodisperse LC core domains were confirmed from polarized optical microscope observations. The final particle morphology was influenced by the cross-linking of the seed particle. When linear PMMA particles, which are not cross-linked, were used as a seed, the microcapsules were distorted after annealing for a few days; however, in the case of cross-linked PMMA particles, the core–shell structure was sustained stably after annealing. Received: 22 November 2000 Accepted: 12 March 2001     

Responsive core-shell latex particles as colloidosome microcapsule membranes

Responsive core-shell latex particles are used to prepare colloidosome microcapsules using thermal annealing and internal cross linking of the shell, allowing the production of the microcapsules at high concentrations. The core-shell particles are composed of a polystyrene core and a shell of poly[2-(dimethylamino)ethyl methacrylate]-b-poly[methyl methacrylate] (PDMA-b-PMMA) chains adsorbed onto the core surface, providing steric stabilization. The PDMA component of the adsorbed polymer shell confers thermally responsive and pH-responsive characteristics to the latex particle, and it also provides glass transitions at temperatures lower than those of the core and reactive amine groups. These features facilitate the formation of stable Pickering emulsion droplets and the immobilization of the latex particle monolayer on these droplets to form colloidosome microcapsules. The immobilization is achieved through thermal annealing or cross linking of the shell under mild conditions feasible for large-scale economic production. We demonstrate here that it is possible to anneal the particle monolayer on the emulsion drop surface at 75-86 °C by using the lower glass-transition temperature of the shell compared to that of the polystyrene cores (～108 °C). The colloidosome microcapsules that are formed have a rigid membrane basically composed of a densely packed monolayer of particles. Chemical cross linking has also been successfully achieved by confining a cross linker within the disperse droplet. This approach leads to the formation of single-layered stimulus-responsive soft colloidosome membranes and provides the advantage of working at very high emulsion concentrations because interdroplet cross linking is thus avoided. The porosity and mechanical strength of the microcapsules are also discussed here in terms of the observed structure of the latex particle monolayers forming the capsule membrane.     

Differences in binding of a cationic surfactant to cross-linked sodium poly(acrylate) and sodium poly(styrene sulfonate) studied by Raman spectroscopy

Raman spectroscopy has been used to investigate the structure of gel-surfactant complexes. Cross-linked sodium poly(acrylate) and sodium poly(styrene sulfonate) were immersed in solutions of the cationic surfactant dodecyl trimethylammonium bromide. During the deswelling process, two distinct regions could be observed for both types of gels. Looking at the Raman spectra, however, for the poly(styrene sulfonate), the surfactant could be found throughout the gel particle, whereas for poly(acrylate), essentially all the surfactant was bound in a surface layer.     

Dumbbell-shaped polyelectrolyte brushes studied by depolarized dynamic light scattering

We present the synthesis and comprehensive characterization of dumbbell-shaped polyelectrolyte brushes (DPB). The core of these particles consists of poly(methyl methacrylate) (PMMA) and poly(styrene) onto which a dense brush shell of poly(styrene sulfonate) is grafted. The morphology of DPB particles is studied in solution by cryogenic-transmission electron microscopy. We demonstrate that well-defined DPB are generated that react to external stimuli such as surfactant and salt concentration. The rotational diffusion and collective relaxations of the DPB particles were monitored by depolarized dynamic light scattering (DDLS). Here we found a new relaxation mode in the DDLS-signal that can be ascribed to collective fluctuations of the polyelectrolyte layer affixed to the surface of the dumbbells.     

Preparation of epoxy‐functionalized polystyrene/silica core–shell composite nanoparticles

Epoxy‐functionalized polystyrene/silica core–shell composite nanoparticles were prepared by the postaddition of glycidyl methacrylate (GMA) via emulsion polymerization. The outermost shell of obtained multilayered core–shell particles was made up of poly(glycidyl methacrylate) (PGMA). A semicontinuous process involving the dropwise addition of GMA was used to avoid demulsification of the emulsion system. The amount of grafted PGMA was quantified by Fourier transform infrared spectroscopy and was altered in a wide range (1–50 wt % to styrene). The binding efficiency was usually high (ca. 90%), indicating strong adhesion between the silica core and the polymer shell. There were approximately four or five original silica beads, which formed a cluster, per composite of nanoparticles whose size was about 60–70 nm. Other main factors of polymerization conditions including the amounts of sodium dodecyl sulfonate and silica are also discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2253–2262, 2004     

Polar Gradient Latex Particles with Hydrophilic Core and Hydrophobic Shell Prepared via Multistep Emulsion Polymerization

Monodisperse polar gradient particles were synthesized via a three‐step emulsion polymerization using poly(butyl acrylate‐methyl methacrylate‐methacrylic acid‐ethylene glycol dimethacrylate) (P(BA‐MMA‐MAA‐EGDMA)) as core, poly(methyl methacrylate‐methacrylic acid‐styrene) (P(St‐MMA‐MAA)) as interlayer and polystyrene (PSt) as shell. The particle growth and encapsulation in each emulsion polymerization step were followed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and conductometric titration. Results indicated that the feeding mode and the interlayer were essential to prepare the polar gradient latex particles with hydrophilic core and hydrophobic shell. The morphologies of the two‐layer core/interlayer and three‐layer core/interlayer/shell particles were observed in TEM micrographs, and the sequential encapsulations of the carboxyl‐containing core and the core/interlayer particles were confirmed by an increase in the particle size as well as an increase in the buried carboxyl percentage.     

丁烯氟虫腈缓释微胶囊的制备及其性能

以丁烯氟虫腈为囊芯化合物,带有相反电性的壳聚糖和海藻酸钠为囊壁材料,采用层层自组装技术制备了丁烯氟虫腈微胶囊,通过流点法筛选出十二烷基苯磺酸钠为丁烯氟虫腈的分散稳定剂。 对制备的微胶囊进行了表征,系统研究了丁烯氟虫腈微胶囊的载药量、包封率、缓释性能和抗光解性能随着组装层数增加的变化规律。 结果表明,组装层数为6~8层的丁烯氟虫腈微胶囊的包封率达到80%以上,达最高释放量所需要的时间为60 h,光解率降到20%以下,综合效果最好。     

悬浮-乳液复合聚合聚苯乙烯-聚甲基丙烯酸甲酯复合粒子的颗粒特性和成粒机理

采用在苯乙烯 (St)悬浮聚合过程中滴加甲基丙烯酸甲酯 (MMA)乳液聚合组分的悬浮 乳液复合聚合方法 ,制备大粒径聚苯乙烯 聚甲基丙烯酸甲酯 (PS PMMA)复合粒子 .研究聚合物粒径分布和颗粒形态的变化发现 ,在St悬浮反应中期滴加MMA乳液聚合组分后 ,聚合体系逐渐由悬浮粒子与乳胶粒子并存向形成单峰分布复合粒子转变 ,最终形成核 壳结构完整的大粒径PS PMMA复合粒子 ;在St悬浮反应初期滴加MMA乳液聚合组分 ,St与MMA一起分散成更小液滴 ,反应后期凝并成非核 壳结构复合粒子 ;在St悬浮反应后期滴加MMA乳液聚合组分 ,PMMA乳胶粒子与PS悬浮粒子基本独立存在 .根据以上结果 ,提出了St MMA悬浮 乳液复合聚合的成粒机理 .     

微胶囊碳酸氢钠合成工艺及热分解特性的研究

利用环氧树脂(EP)对碳酸氢钠(SB)进行包覆合成微胶囊碳酸氢钠,通过红外光谱仪(FTIR)、扫描电子显微镜(SEM)、差示扫描量热计(DSC)和热重分析仪(TG)等表征手段,分析了合成反应温度、环氧树脂与碳酸氢钠的质量比对微胶囊碳酸氢钠的结构、表面形貌特征以及热分解特性的影响。结果表明:当反应温度为70℃,环氧树脂与碳酸氢钠的质量比为1∶5时,碳酸氢钠的改性效果较理想,表面形貌比较规整,起始分解温度由118℃提高至154.9℃,分解温度区间从46.3℃缩短到24.8℃;使用微胶囊碳酸氢钠制备的微发泡聚丙烯材料,发泡质量较理想。     

Protein adsorption on polymer-modified silica particle surface

Silicon substrate surface and silica particle surface were modified with five kinds of polymers, poly(2-methoxyethyl methacrylate) (pMEMA), poly(2-hydroxyethyl methacrylate) (pHEMA), poly(acrylamide) (pAAm), poly(methyl methacrylate) (pMMA), and poly(styrene) (pSt), using a combined polymerization of surface-initiated polymerization that gives dense polymer chain layers and atom transfer radical polymerization (ATRP) that yields polymers with a narrow molecular weight distribution. Measurements of water contact angle and polymer chain amount on the modified silicon substrate surface and adsorption amounts of proteins (albumin and fibrinogen) on the modified silica particle surface revealed that the amount of polymer on the modified surface greatly affects the suppression of protein adsorption on the surface.