Microwave-assisted synthesis of poly(urea-formaldehyde)/lauryl alcohol phase change energy storage microcapsules

In this study, lauryl alcohol suitable for thermal energy storage applications was microencapsulated in a poly(urea-formaldehyde) shell. The microcapsules were prepared by microwave-assisted in situ polymerization. The morphology and particle size of the poly(urea-formaldehyde)/lauryl alcohol phase change energy storage microcapsules(UF/LA PCESMs) were analyzed using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering. The latent heat storage capacities of lauryl alcohol and UF/LA PCESMs were determined using differential scanning calorimetry. The chemical composition of the microcapsules was characterized using Fourier transform infrared spectroscopy. All of the results show that UF/LA PCESMs were synthesized successfully and that the latent heat storage capacity and encapsulation efficiency were 156.0 J/g and 75.0%, respectively, and the diameter of each microcapsule was around 150 nm.     

脲甲醛缩聚物制备电子墨水微胶囊研究

在原位聚合法制备脲甲醛树脂微胶囊的过程中 ,使用水溶性低分子量脲甲醛缩聚物代替传统的脲甲醛预聚体 (一羟甲基脲、二羟甲基脲 )作为反应单体 ,由于脲甲醛缩聚物比后者更容易吸附在分散相液滴表面 ,解决了用原位聚合法制备脲甲醛微胶囊所常有的结块、粘连、表面粗糙、产率低的问题 .研究了低分子量脲甲醛缩聚物水溶液的粘度特征和表面活性及其与胶囊包封率的关系 .使用这种方法制备出了电子墨水微胶囊     

Chemical and structural modification of polymers by matrix polymerization

The condensation polymerization of urea and formaldehyde in water in the presence of a macromolecular matrix, polyacrylic acid, as well as properties of composites obtained by the matrix polymerization, have been studied. The chemical structure of the urea-formaldehyde polymer was changed by the presence of the matrix. The products of matrix polymerization are composites consisting of a stoichiometric polycomplex of polyacrylic acid with the urea-formaldehyde polymer and an excess of one of the components, depending on the initial composition of the system. Introduction of matrix macromolecules into the reacting system leads to a fibrillized structure of the urea-formaldehyde polymer. The polycomplex, as well as composites with high content of polyacrylic acid, are glasses characterized by high compressive strength and ability to forced elastic deformation. They swell in water. The highly cooperative character of potentiometric titration curves for swollen gels and the quantitative yield in intermolecular amidation indicate an ideal structure of the polycomplex stabilized by hydrogen and ionic-type bonds.     

紫外光固化自修复剂的微胶囊化及智能防腐蚀涂层的制备

利用在水相中原位生成的聚脲甲醛沉淀吸附在可见紫外光固化组份构成的油相表面,制备了包覆自修复剂的脲醛树脂（PUF）微胶囊. 光学显微镜及SEM表明,PUF微胶囊尺寸为118-663 μm,与PUF 形成过程中的搅拌速度有关. 在中等搅拌速度（600 r/min）时,可以得到最高的包覆率（97.52wt%）和产率（65.23wt%）. 将此微胶囊掺入水性聚氨酯乳胶中制成的涂层表面受损后,在紫外光照射下可以进行自修复,具有优异的金属防腐蚀性能.     

Efficient Entrapment of Oxirane Ring Containing Compounds in Thermally Stable Poly(urea-formaldehyde) Polymer Shell Wall

This article aims to address the problems associated with the encapsulation of oxirane ring containing compounds in poly(urea-formaldehyde) (PUF) shell for application in self-healing composite systems. The main objectives were to produce non-agglomerated, stable microcapsules, and to control the pH drop during the encapsulation via oil-in-water emulsion polymerization. In the modified method; two stage additions of urea and formaldehyde monomers, core to shell ratio, weight percent and combination of two surfactants/emulsifiers were altered to produce the desired product. Analysis was done with optical microscope (OM), scanning electron microscopy (SEM), FTIR, particle size analyzer, and thermogravimetric analysis (TGA). The pH drop was confirmed by using a common epoxy resin, an epoxy functionalized polydimethylsiloxane (E-PDMS), and epoxidized palm oil (EPO) as cores. The modified oil-in-water emulsion polymerization of PUF was effective in preventing the pH drop during the encapsulation and a product stable for more than 3 months with less agglomeration was produced. The method produced microcapsules having diameters less than 100 μm at lower agitation rates. The modified method is only applicable to epoxy resin and not for compounds like amine hardeners. The use of stable microcapsules in self-healing coatings can lead towards cost reduction implied for repair and maintenance purposes.     

Generation of core-shell microcapsules with three-dimensional focusing device for efficient formation of cell spheroid

We present a microfluidic device generating three-dimensional (3D) coaxial flow by the addition of a simple hillock to produce an alginate core-shell microcapsule for the efficient formation of a cell spheroid. A hillock tapered at downstream of the two-dimensional focusing channel enables outside flow to enclose the core flow. The aqueous solution in the core flow was focused and surrounded by 1.8% alginate solution to be solidified as a shell. The double-layered coaxial flow (aqueous phase) was broken up into a droplet by the shear flow of oleic acid (oil phase) containing calcium chloride for the polymerization of the alginate shell. The droplet generated from the laminar coaxial flow maintained a double-layer structure and gelation of the alginate solution made a core-shell microcapsule. The shell-thickness of the microcapsule was adjusted from 8-21 μm by the variation of two aqueous flow rates. The inner shape of the shell was almost spherical when the ratio of the water-glycol mixture in the core flow exceeded 20%. The microcapsule was used to form a spheroid of embryonic carcinoma cells (embryoid body; EB) by injecting a cell suspension into the core flow. The cells inside the microcapsule aggregated into an EB within 2 days and the EB formation rate was more than 80% with strong compaction. The microcapsule formed single spherical EBs without small satellite clusters or a bumpy shape as observed in solid microbeads. The microfluidic chip for encapsulation of cells could generate a number of EBs with high rate of EB formation when compared with the conventional hanging drop method. The core-shell microcapsule generated by 3D focusing in the microchannel was effective in forming large number of spherical cell clusters and the encapsulation of cells in the microcapsule is expected to be useful in the transplantation of islet cells or cancer stem cell enrichment.     

Preparation of biodegradable microcapsules through an organic solvent‐free interfacial polymerization method

We prepared microcapsules through an organic solvent‐free interfacial polymerization method, which avoids the release of volatile organic compounds arising from conventional interfacial polymerization methods for microencapsulation. These microcapsules have single and narrow particle size distribution and are spherical pellets with smooth and intact shell, and own excellent biodegradability. Additionally, these biodegradable microcapsules have a higher encapsulation efficiency compared with the microcapsules prepared through conventional interfacial polymerization method and possess sustained and controlled release of core materials.     

高性能自修复微胶囊预聚物组成的研究

为了指导高性能自修复微胶囊的制备研究, 利用偏光显微熔点仪、红外光谱和核磁共振氢谱定量研究了微胶囊预聚物组成随反应条件如反应温度、pH 值和甲醛-尿素物质的量比的变化. 研究结果表明, 升高体系温度和pH 值都会显著促进副反应的发生从而降低产物中二羟甲基脲的产率; 而提高甲醛-尿素的物质的量比, 二羟甲基脲的产率增加,同时三羟甲基脲的产率降低. 此外, 还研究了升温过程中反应体系的温度变化情况. 研究发现: 升温速率一定时, 反应体系的温度变化均匀, 没有温度骤变阶段.     

Uniform encapsulation of fine inorganic powder with soapless emulsion polymerization

The encapsulation of inorganic powder of submicron sizes was attempted with soapless emulsion polymerization of methyl methacrylate in water in the presence of the powder. The powders used were barium sulfate and calcium carbonate. The polymerizations were initiated by potassium persulfate and by sodium bisulfite-oxygen redox reaction. The encapsulation state of the powder with the polymer formed varied considerably with the initiators used. With potassium persulfate initiator the powder surface was partially or totally covered by polymer particles, while with redox initiator under air atmosphere the powder surface was well encapsulated with a film-like polymer layer. From the differences in the encapsulation states, an encapsulation mechanism is suggested for each initiator system. Based upon this mechanism, a new encapsulation process capable of covering uniformly fine powders with a film polymer is proposed. An important factor in the new process is the addition of an extremely small quantity of a surfactant into the reaction system prior to the polymerization.     

Study of the interfacial polycondensation of isocyanate in the preparation of benzalkonium chloride loaded microcapsules

The preparation of benzalkonium chloride loaded microcapsules was performed by interfacial polycondensation of isocyanates. The present study was made in order to clarify parameters affecting microcapsule wall formation during the course of polymerization. The results presented here show that many interrelated parameters are involved during the microcapsule formation. Each individual component introduced in the preparation was shown to have an effect either on the morphology of the microcapsules or on the mechanical resistance. Benzalkonium chloride seemed to interact mainly in the interfacial polymer precipitation step through a salt effect, or influence the polycondensation reaction rate acting as a catalyst. A contribution of the hydroxylic functions of the surfactant in the polycondensation reaction of the isocyanate was also highlighted. Finally, the organic phase composition was found to be able to modulate the reactivity of hydroxylic functions of the surfactant, leading to very slow reactions in pure xylene. These effects were related to the characteristics of the microcapsules obtained according to different compositions of the formulation system.     

Kinetics and activity distribution of grease coencapsulated with hemoglobin within polyamide membranes

A 91.5% mass yield of urease and hemoglobin (Hb), co-encapsulated within polyamide membranes, was determined spectrophoto-metrically. The specific activity yield of microencapsulation was 84%, twofold higher than values previously reported, as a result of optimization of encapsulation conditions. The kinetic parameters and pH activity profiles of intracapsular urease were determined to be similar to those corresponding to the free enzyme. Similar activities were also observed for intact and microcapsule homogenate, indicating minimal mass transfer and diffusional limitation. The active configuration of the enzyme appears to remain intact upon microencapsulation. The application of a kinetic model for encapsulated urease further indicated that the kinetics were reaction-controlled with minimal mass transfer restrictions.     

Coordination polymerization in water affording amorphous polyethylenes

The coordination polymerization of ethylene in water as a reaction medium was studied. Rubbery amorphous branched polyethylene was obtained when a known cationic diimine-substituted methyl complex was employed as a catalyst precursor. High rates of up to 900 TOh(-1) (turnover frequency) were observed. In contrast to solution polymerization in an organic solvent, the rate of suspension polymerization in water increases greatly with ethylene pressure in the range up to 20 bar; this indicates control of the polymerization rate by the concentration of the olefin monomer at the catalytically active site. The effect and mode of mass transfer phenomena were studied. A high catalyst stability in the aqueous coordination polymerization was observed. It was found to be due to an "encapsulation" of the water-insoluble catalyst precursor in the hydrophobic amorphous polymer during the polymerization reaction, and this resulted in strongly restricted accessibility for the aqueous phase. Surprisingly, exposure of the water-stable catalyst precursor to ethylene monomer in solution in the presence of water resulted in immediate decomposition. Polymer microstructure, and thermal and mechanical properties were investigated. The different degree of branching, molecular weight, and corresponding macroscopic properties of the polymers obtained in water as a reaction medium versus solution polymerization in methylene chloride under the same conditions are due to the different phase behavior during polymerization (suspension vs. solution), as opposed to an effect of water on the catalytically active centers.     

Dicarboxylic acids amides as an acceptor of formaldehyde in urea-formaldehyde resins

The possibility of reducing the content of free formaldehyde in urea-formaldehyde resin by introducing into the final resin composition of diphthalic and dimaleic acids amides was studied. It was found that the amides synthesized are able to participate in formaldehyde addition as well as in its polymerization and they are effective acceptor of formaldehyde in urea-formaldehyde resins.     

Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation

This Article describes a new microencapsulation method based on a Pickering emulsion templated interfacial atom transfer radical polymerization (PETI-ATRP). Cationic LUDOX CL nanoparticles were coated electrostatically with an anionic polymeric ATRP initiator, poly(sodium styrene sulfonate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate) (PSB), prepared by radical copolymerization of sodium styrene sulfonate and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). The resulting PSB-modified CL particles were surface active and could be used to stabilize oil-in-water Pickering emulsions. ATRP of water-soluble cross-linking monomers, confined to the oil-water interface by the surface-bound PSB, then led to nanoparticle/polymer composite shells. This method allowed encapsulation of core solvents (xylene, hexadecane, perfluoroheptane) with different solubility parameters. The microcapsule (MC) wall chemistry could accommodate different monomers, demonstrating the versatility of this method. Double-walled MCs were formed by sequentially carrying out PETI-ATRP and in situ polymerization of encapsulated monomers. The double-walled structure was verified by both transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).     

辣素微胶囊的原位聚合法制备与热降解动力学

在乳液体系中,以尿醛为壁材,以原位聚合法制备了辣素同系物———N-香草基壬酰胺微胶囊。红外光谱证实了尿醛的形成,X-射线衍射显示了同样作为半晶高分子囊壁,尿醛包裹囊心前后出现的结构晶型差异。根据吸附等温曲线假设微胶囊为紧密堆积形式,对于尿醛单体颗粒和尿醛微胶囊的TGA,采用Achar-B rind ley-Sharp-W endworth方法,对两者进行热重数据的处理,以作图法求得了动力学参数,确定了热降解动力学模式函数,回归系数良好。TGA求解的活化能数据证明由于晶型差异,导致单体与微胶囊热稳定性不同,从而与XRD结论一致。     

Preparation and characterization of poly(melamine-formaldehyde) microcapsules filled with propisochlor

A novel propisochlor microcapsules suspension (CS) was prepared via in-situ polymerization. The preparation of melamine-formaldehyde resin microcapsules containing propisochlor with different ratios of core-shell material was investigated. The synthesized microcapsules were characterized by Fourier Transform Infrared spectrometer, Scanning Electron Microscope, Ultraviolet spectrometry, Thermogravimetric analyses and particle size analyzer. As the ratio of core/shell was 1, the diameter of the prepared microcapsules was the smallest (3.55?µm), while narrowest size distribution (span: 1.19) and the melamine formaldehyde microcapsules possessed the highest encapsulation efficiency (93.26%). The surface of the microcapsules was smooth and the microcapsules had poor adhesion. These microcapsules had compact microstructures and global shapes, which had a good thermal stability and propisochlor could be preserved better in the poly(melamine-formaldehyde) (PMF) microcapsules. These results indicated that the prepared microcapsule had better performance. Additionally, the propisochlor was easily degraded through microorganisms and had a short half-life. The microcapsule suspension of propisochlor hasn’t been researched yet. Therefore, it is significant to prepare microcapsule suspension. The technology of controlled release has effectively prolonged the persistence of active ingredients. More importantly, there is no use of organic solvents in the preparation of microcapsules suspension, which avoided the pollution of solvents to the ecological environment.     

Polyaniline microsphere encapsulated by poly(methyl methacrylate) and investigation of its electrorheological properties

Microspheres consisting of a poly(methyl methacrylate) (PMMA) shell wrapping the conductive polyaniline (PANI) particle as a core were prepared by an in-situ suspension polymerization method and then adopted as an electrorheological (ER) material. The polymerization reaction and encapsulation were confirmed by Fourier transform infrared spectrum analysis. The rod-like PANI particles were synthesized via an emulsion polymerization protocol and observed by transmission electron microscopy. In addition, a spherical shape of encapsulated PANI/PMMA (core/shell) microspheres was observed by scanning electron microscopy. The thermal stability of PANI/PMMA particles was examined by use of thermogravimetric analysis. The PANI/PMMA particle-based suspension in silicone oil exhibited typical ER behavior. The conductivity of PANI/PMMA particles was much lower than that of the rod-like PANI.     

Encapsulation of β-cyclodextrin by in situ polymerization with vinyl chloride leading to suppressing the migration of endocrine disrupting phthalate plasticizer

We performed the encapsulation of β-cyclodextrin (β-CD) in PVC by in situ polymerization with vinyl chloride monomer (VCM), and investigated the effect of CD encapsulation on the suppression of dioctyl phthalate (DOP) migration suspected as endocrine disruptor. β-CD was partially modified with 3-(methacryloxy)propyl trimethoxysilane and modified β-CD (MCD) was then encapsulated in PVC through suspension polymerization via radical reaction between double bonds MCD and VCM. Resulting MCD-encapsulated PVC (MCD_x-PVC) exhibited the similar morphology and characteristics to commercial PVC. For MCD_x-PVCs plasticized with DOP, they showed the considerably suppressed DOP migration as well as the similar optical and mechanical properties to conventionally plasticized PVC. In particular, the plasticized MCD_x-PVCs exhibited the superior suppression of DOP migration compared to the plasticized PVC where MCD and DOP were introduced by conventional melt mixing. Therefore, the encapsulation of MCD in PVC is thought to be an effective approach to producing the ecological PVC material.     

生物农药微胶囊壁材料研究

用原位聚合法对生物农药阿维菌素进行包囊,然后制备微胶囊制剂,并对用于该制剂的两种高分子囊壁材料-三聚氰胺甲醛树脂和脲醛树脂的性能进行了研究。结果表明,两种树脂皆为较好的生物农药用微胶囊缓释剂型的囊壁材料,其制备工艺简单,具有良好的稳定性、粒径大小与分布、悬浮性、缓释性等,包封率均达80％以上。其中三聚氰胺甲醛树脂悬浮性较脲醛树脂更好,缓释性更持久。     

Entrapment of a weak polyanion and H+/Na+ exchange in confined polyelectrolyte microcapsules

An approach for the entrapment of a polyanion by polyelectrolyte microcapsules is reported. It is based on a reversal changing of microcapsule wall permeability from neutral to basic pH. Polyelectrolyte microcapsules were templated on latex (polystyrene) particles by the layer-by-layer adsorption of oppositely charged polymers of sodium poly(styrene sulfonate) and poly(allylamine hydrochloride), followed by core removal using tetrahydrofuran. In alkaline conditions, the microcapsules swell and become permeable for polymers. During encapsulation, the addition of salt ions increases the amount of the polymer encapsulated and contributes to its protonation because of redistribution of H+ ions across a semipermeable microcapsule wall. The redistribution of small ions across the microcapsule wall was tuned by adding salt according to the Donnan equilibrium and was characterized by H+ sensitive dyes.