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.     

Synthesis and thermal properties of poly(n‐butyl acrylate)/n‐hexadecane microcapsules using different cross‐linkers and their application to textile fabrics

This study focused on the preparation, characterization, and determination of thermal properties of microencapsulated n‐hexadecane with poly(butyl acrylate) (PBA) to be used in textiles with heat storage property. Microcapsules were synthesized by emulsion polymerization method, and the particle size, particle size distribution, shape, and thermal storage/release properties of the synthesized microcapsules were analyzed using Fourier‐transform infrared spectroscopy, scanning electron microscopy, and differential scanning calorimetry techniques. Allyl methacrylate, ethylene glycol dimethacrylate, and glycidyl methacrylate were used as cross‐linkers to produce unimodal particle size distribution. MicroPBA microcapsules produced using allyl methacrylate cross‐linker were applied to 100% cotton and 50/50% cotton/polyester blend fabrics by pad‐cure method. The mean particle size of microcapsules ranges from 0.47 to 4.25 μm. Differential scanning calorimetry analysis indicated that hexadecane in the microcapsules melts at nearly 17°C and crystallizes at around 15°C. The contents of n‐hexadecane of different PBA microcapsules were in the range of 27.7–50.7%, and the melting enthalpies for these ratios were between 65.67 and 120.16 J/g, respectively. The particle size and thermal properties of microcapsules changed depending on the cross‐linker type. The cotton and 50/50% cotton/polyester blend fabrics stored 6.56 and 28.59 J/g thermal energy, respectively. The results indicated that PBA microcapsules have the potential to be used as a solid‐state thermal energy storage material in fabrics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Designing of polyamidoamine-based polyurea microcapsules containing tung oil for anticorrosive coating applications

A novel method for the fabrication of robust polyurea microcapsules containing tung oil as a core material was developed for self-healing anticorrosive coating application. Well-distinct microcapsules with polyurea as a shell were prepared by reacting hexamethylene diisocyanate trimer with 0.0 G polyamidoamine (PAMAM) via interfacial polymerization technique. Fourier transform infrared spectroscopic analysis was performed to elucidate the chemical structure of microcapsules as well as to confirm successful encapsulation of core by the polyurea shell. Surface morphology, particle size, distribution of particle size, thermal, and mechanical properties of the prepared PAMAM-based polyurea microcapsules were compared with microcapsules that were prepared using diethylenetriamine (DETA) and triethylenetetramine (TETA). The prepared microcapsules were embedded with acrylic polyol-based polyurethane (PU) coatings to ensure anticorrosive performance. The immersion study of self-healing PU coatings loaded with 5% PAMAM-based polyurea microcapsules possesses satisfactory anticorrosive property under an accelerated corrosion process in 5% NaCl salt solution.     

Efficient preparation and characterization of paraffin-based microcapsules by emulsion polymerization

Microencapsulated phase-change materials (MEPCMs) with paraffin as the core and poly(methyl methacrylate) (PMMA) and PMMA copolymers as the shell were prepared by emulsion polymerization using redox initiators at low temperatures. Fourier transform infrared spectroscopy was used to characterize the chemical composition of MEPCMs. The thermal properties and thermal stabilities of MEPCMs were tested by differential scanning calorimetry and thermogravimetric analysis. The morphologies and sizes of the microcapsules were investigated by scanning electron microscopy and particle size distribution analysis. The results indicated that the yield of microcapsules is as high as 96.2%, and the encapsulation efficiency of paraffin is nearly 100% when the paraffin content in MEPCM is 70%. The MEPCMs have good stability: the leakage ratios of MEPCMs can be less than 1% after 50 heating–cooling cycles. Therefore, the microencapsulation of paraffin using redox initiators has good production and application prospects. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47552.     

Microencapsulation of triglycidyl isocyanurate by solvent evaporation method for UV and thermal dual‐cured coatings

Triglycidyl isocyanurate (TGIC), a thermal curing agent, was encapsulated with poly(methyl methacrylate) with small particle size and narrow distribution for the application in acrylic resins to prepare one‐package UV and thermal dual‐cured coatings. Investigation of the wettability and thermal properties suggests that the microcapsules have better compatibility with acrylic resins and thermal stability as compared to pure TGIC. Results of the release performance experiments indicate good storage stability at 25°C and a quick release of vast TGIC at 120°C for the microcapsules. The UV‐thermal dual‐cured coatings prepared with the microcapsules exhibit a fast, even and complete hardening at 130°C together with an excellent adhesion to the mild steel panels. The results presented here show an application potential of the microcapsules in UV and thermal dual‐cured paints. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41008.     

Poly(divinylbenzene) Microencapsulated Octadecane for Use as a Heat Storage Material: Influences of Microcapsule Size and Monomer/Octadecane Ratio

Poly(divinylbenzene) (PDVB) microencapsulated octadecane (OD) (PDVB/OD) used as heat storage material were prepared by suspension polymerization at 70°C using benzoyl peroxide and polyvinyl alcohol as initiator and stabilizer, respectively. The influence of microcapsule size and divinylbenzene (DVB)/OD weight ratio on the microcapsule shape and thermal properties of encapsulated OD were considered. Thermal properties and thermal stability of PDVB/OD microcapsules were determined using differential scanning calorimeter (DSC) and thermogravimetric analyzer. The optical micrographs and scanning electron micrographs showed that the microcapsules have spherical shape only in the case of 50/50 (%w/w) of DVB/OD whereas they were nonspherical with the decreasing of DVB content. However, the core materials were still well encapsulated even increasing the OD content to 70%wt. From DSC analysis, in all cases, the melting temperature of encapsulated OD (28°C) was almost the same as that of bulk OD (30°C), yet it was quite different in the case of crystallization temperature (≤ 19°C and 25°C for encapsulated and bulk OD, respectively). The latent heats of melting and crystallization of encapsulated OD, in all conditions, were reduced from those of bulk OD (242 and 247 J/g, respectively).     

Preparation and characterization of paraffin microcapsules for energy-saving applications

A series of microencapsulated phase-change materials (PCMs) with styrene–divinyl benzene shells composed of an n-octadecane (OD or C₁₈)–n-hexadecane (HD or C₁₆) mixture as the core were synthesized by an emulsion polymerization method. The effects of the core/shell ratio (C/S) and surfactant concentration (C_surf) on the thermal properties and encapsulation ratios of the PCMs were investigated. The chemical structures and morphological properties of the microcapsules were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy analysis, respectively. The characteristic peaks of the paraffin mixtures and shell material located in the FTIR spectrum of the microencapsulated PCMs proved that the encapsulation of the PCM mixture was performed successfully. The thermal properties of the paraffin microcapsules were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis. DSC analysis demonstrated that the microcapsules containing the maximum amount of paraffin mixture (C/S = 2:1) and the minimum C_surf (45 mmol/L) had the highest latent heat value of 88 kJ/kg and a latent heat of temperature of 21.06°C. Moreover, the maximum encapsulation ratio of the paraffin mixture was found to be 56.77%. With respect to the analysis results, the encapsulated binary mixture, which consisted of OD–HD with a poly(styrene-co-divinyl benzene) shell, is a promising material for thermal energy storage applications operating at low temperatures, such as in the thermal control of indoor temperatures and air-conditioning applications in buildings for desirable thermal comfort and energy conservation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47874.     

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...     

Characteristics,Stability, and Release of Peanut Sprout Extracts in Powdered Microcapsules by Spray Drying

This study was carried out to investigate the characteristics of powdered microcapsules from peanut sprout extracts prepared by spray drying. The microcapsules were made from medium-chain triglyceride (MCT) as primary coating material and whey protein concentrate (WPC) or maltodextrin (MD) as selected secondary coating materials. The microcapsule studies conducted were microphotograph, scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR), particle size, moisture contents, sorption, zeta potential, storage stability, and in-vitro study. The surface of microcapsules coated with WPC were rough and smooth, and particle size ranged from 2.86 to 8.59 µm. An FT-IR study revealed that absorption bands at 1,537 and 1,657 cm^?1 of microcapsules can be attributed to the protein amide I and II bands of WPC overlapped by the conjugated C?C. The moisture content was 1.33% in the microcapsules coated with WPC. The moisture sorption increased until 18% at the 90% RH. The yield of peanut sprout extracts from microcapsules was 89.01%. In the in-vitro study, the microcapsules released 2.48 and 6.01% at pH 2.0 and 4.0, respectively, in simulated-gastric fluid, and 61.07 and 89.24% at pH 6.0 and 8.0, respectively, in simulated-intestinal fluid. The preservation rate of the microcapsules dropped down to 60.43% from 89.01% during six months of storage. The stability of peanut sprout extracts in the microcapsules was over 80% at 4 and 20°C during 10-day storage. The zeta-potential of microcapsules was stable with ?30 mV. Based on the data obtained from the present study, the powdered peanut-sprout-extract microcapsules coated with WPC exhibited high stability during storage. Therefore, the powdered microcapsules by spray drying may be useful as a functional ingredient.     

Preparation of PLA-Coated Energy Storage Microcapsules and Its Application in Polyethylene Composites

With polylactic acid (PLA) resin as walls and paraffin wax as core substances, phase change microcapsules were prepared based on solvent evaporation method. The energy storage microcapsules (ESM) agents had a mean diameter of about 5 ～ 10 µm. Moreover, the thermal properties of the ESM agents were measured by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Different types of PE composites were prepared with different amounts of these additives. The energy storage properties of PE/ESM composites were improved compared with that of pure PE and PE/paraffin wax composites. However, the tensile properties of these composites showed remarkable decrease.     

Thermal and morphological stability of polystyrene microcapsules containing phase‐change materials

Polystyrene microcapsules with paraffin wax as the active agent [phase‐change material (PCM)] were produced by a Shirasu porous glass emulsification technique and a subsequent suspension‐like polymerization process. The suitability of the obtained microcapsules for textile applications was studied. The thermal properties, surface morphology, and structural stability of the PCM microcapsules were investigated with differential scanning calorimetry, thermogravimetric analysis, and environmental scanning electron microscopy. The microcapsules could be used without any appreciable damage or irreversible changes in their integrity until 135°C. Furthermore, these microcapsules were heat‐resistant and could endure the curing conditions of textile coating up to 140°C for 30 min. In addition, the stability of the microcapsules under common laundering conditions was tested. It was confirmed that the microcapsules were durable enough and maintained their stability during stirring in hot water and alkaline solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In-situ polyurethane/polyacrylate microemulsion formation: the effects of acrylic content in wood coating application

In-situ surfactant-free emulsion polymerization was utilized to prepare polyacrylate/polyurethane (PUA) microemulsions in the absence of surfactant and organic solvent. For this purpose, PUA with higher acrylate content was successfully prepared, with the aim to reduce the coating cost. The dynamic light scattering results showed that the particle size of PUA microemulsion displayed a unimodal distribution and the particle size was ranged from 33 to 61 nm. In comparison with PUA prepared with conventional miniemulsion polymerization, the particle size distribution coefficient dropped by one order. Atomic force microscopy, together with thermogravimetric analyzer, demonstrated good compatibility and interaction between PU and acrylic components, and no phase separation was detected even at 58 wt% acrylic content. With the incorporation of acrylic component, the thermal stability and maximum stress were improved. The maximum stress greatly increased from 4.6 to 30.9 MPa, and the maximum stress of in-situ PUA was nearly three times larger than that of PUA prepared by miniemulsion polymerization. The effects of acrylic content on water resistance, pencil hardness, adhesion, and impact strength of wood coating were evaluated. With increasing the acrylic content, the water resistance and pencil hardness increased, though the impact strength of in-situ PUA films was slightly reduced.     

相变微胶囊的制备及其在涂料中的应用研究

实验采用界面聚合法,以2,4-甲苯二异氰酸酯(TDI)与四乙烯五胺(TEPA)的反应物为壁材包覆硬脂酸丁酯制成聚脲微胶囊相变材料,同时对微胶囊进行了FTIR、DSC和SEM等性能检测。并将此自制微胶囊作为填料,添加到防锈涂料中,对其进行相应的性能检测及表征,结果表明:防锈涂料相变温度19.2℃,相变焓65.5 J/g,具有一定的调温性能。     

Preparation of coated thermo‐regulating textiles using Rubitherm‐RT31 microcapsules

Spherical microcapsules with a 49 wt % of Rubitherm^® RT31 were successfully synthesized by means of suspension‐like polymerization to be used for textile applications in summer conditions. Microcapsules were fixed into seven fabric substrates for different textile applications by a coating technique without deteriorating original functionalities of the textiles. Thermal performance of different coated textiles with 35 wt % of microcapsules was evaluated by differential scanning calorimetry (DSC) and infrared thermography (IR) techniques and the physical characteristics of textiles with thermo‐regulating properties were examined by environmental scanning electron microscopy (ESEM). It was observed that all treated textile substrates allow to obtain thermo‐regulating properties with acceptable latent heat storage capacities. Results also indicated that the presence of microcapsules containing Rubitherm^® RT31 produces a significant thermal insulation effect during a cold to warm transition (20–45°C). Thus, this kind of microcapsules can be used to obtain textiles with thermal comfort‐related properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Model-free kinetic analysis of thermal behavior of urea-formaldehyde microcapsules

In this study, experimental and analytical investigations were conducted concerning kinetics of thermal reactions of urea-formaldehyde microcapsules (UFM). Microencapsulated phase change materials were synthesized via in-situ polymerization using UF resin as shell and drying oil as core, and were characterized by scanning electron microscope (SEM), particle size analysis (PSA) and Fourier transform infrared analysis (FTIR). Accordingly, model-free kinetics (MFK) was used to determine the kinetics of the thermal behavior of UFM. Therefore, Thermogravimetry analysis was conducted at different heating rates of 3, 5, 7, and 10 °C/min. The apparent activation energy was obtained by MFK, which led to identify the reaction mechanisms. The results revealed that there are two stages for degradation of the synthesized microcapsules. Addition of the oil core in the UF microcapsules has hindered one stage of the suggested three stages of the pyrolysis process of UF based resins and the two stages were unified as a single extended stage. Additionally, the measured activation energy showed a low value of 20 kJ/mol due to the presence of oil in the UF microcapsules.     

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。     

Preparation and properties of bisphenol A epoxy resin microcapsules coated with melamine–formaldehyde resin

Microcapsules containing epoxy resins have potential applications, such as in adhesive, electronic packaging, and self-healing polymeric composites. A series of microcapsules were prepared by in situ polymerization with poly(melamine–formaldehyde) as the shell materials and a mixture of diglycidyl ether of bisphenol A and epoxy diluent as the core substances. Morphology, chemical structure, mean particle size, and thermal properties of the microcapsules were studied by means of optical microscope, Fourier transform infrared spectroscopy, laser particle size analyzer, and microcomputer differential thermal balance, respectively. Effects of kind of epoxy diluent, surfactant type, emulsifier concentration, and emulsifying rate on the physical properties of microcapsules were investigated. Results indicate that the formation of microcapsules is affected by the epoxy diluent type and surfactant type. The highest core content of the resultant microcapsules is about 88 wt% and average diameters of the capsules range from 67 to 201 μm, which can be adjusted by changing the emulsifier concentration and emulsifying rate. Thermo gravimetric analysis indicated that the prepared microcapsules experienced excellent stability up to 235 °C.     

Effect of different amounts of surfactant on characteristics of nanoencapsulated phase-change materials

Phase-change nanocapsule particles are successfully synthesized by the two-step miniemulsion polymerization method. Urea–formaldehyde resin is used as the shell material. Hexadecane is used as the core material. The particle size distribution and the surface morphology of nanocapsules are characterized by laser particle size analyzer, optical and scanning electron microscopy. The thermal properties are investigated by differential scanning calorimeter. The effects of the amounts of surfactant (AS) on the properties of prepared nanocapsules are also investigated. The results indicated that the nanocapsules have smooth surface and the mean particle size is about 270 nm; nano-structure of capsules has not changed dramatically after being heated at 100 °C for 72 h; The phase-change enthalpy of nanocapsules increases from 114.6 to 143.7 J/g with the increasing of the AS, but the mean particle diameter decreases from 285 to 253 nm; The degree of undercooling of hexadecane decreases about average 94% after being encapsulated in capsules.     

石蜡相变微胶囊的制备及性能研究

摘 要：以石蜡为芯材,蜜胺树脂(MF)为壁材,采用原位聚合法制备了石蜡相变微胶囊。采用傅里叶红外光谱仪（FT-IR）、扫描电子显微镜（SEM）、激光粒度分析仪和差示扫描量热仪(DSC)对微胶囊的性能和形貌进行了分析和表征,讨论了甲醛与三聚氰胺的摩尔比（F/M）对微胶囊性能和形貌的影响。实验结果表明,F/M摩尔比大于4时,微胶囊之间发生粘结,出现了团聚现象;微胶囊的相变温度略高于芯材石蜡,随着F/M摩尔比增加,微胶囊的相变潜热降低。