Preparation of organic/inorganic hybrid and hollow particles by catalytic deposition of silica onto core/shell heterocoagulates modified with poly[2-(N,N-dimethylamino)ethyl methacrylate

The organic/inorganic hybrid particles PSt/P(St-CPEM)(θ)-g-PDMAEMA/SiO(2) were prepared by catalytic hydrolysis and subsequent polycondensation of tetraethoxysilane in the poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA) layers grafted on the PSt/P(St-CPEM)(θ) core/shell heterocoagulates. The micron-sized PSt core and the submicron-sized P(St-CPEM) shell particles bearing ATRP initiating groups were synthesized by dispersion polymerization of styrene (St) and emulsifier-free emulsion polymerization of St with 2-chloropropionyloxyethyl methacrylate (CPEM), respectively. The raspberry-shaped PSt/P(St-CPEM)(θ) heterocoagulates with a controlled surface coverage (θ=0.51, 0.81) were prepared by hydrophobic coagulation between the core and the shell particles in an aqueous NaCl solution near the T(g) of P(St-CPEM). Surface modification of heterocoagulates was carried out by ATRP of DMAEMA from the shell particles adsorbed on the core particles. Silica deposition was performed by simply adding tetraethoxysilane to a water/methanol dispersion of PSt/P(St-CPEM)(θ)-g-PDMAEMA. The SEM and TGA revealed that the resulting PSt/P(St-CPEM)(θ)-g-PDMAEMA/SiO(2) composites maintain a raspberry-like morphology after deposition of silica onto the PDMAEMA layer grafted on heterocoagulates. The micron-sized, raspberry-shaped or the submicron-sized, hole-structured silica hollow particles were obtained selectively by thermal decomposition of the PSt/P(St-CPEM)(θ)-g-PDMAEMA/SiO(2). The oriented particle array was fabricated by dropping anisotropically perforated silica particles onto a glass substrate settled at the bottom of a bottle filled with chloroform.     

Biomimetic silver-containing colloids of poly(2-methacryloyloxyethyl phosphorylcholine) and their film-formation properties

The synthesis of stable dispersions of hybrid colloids comprising copolymers of biocompatible 2-hydroxyethyl methacrylate (HEMA) and zwitterionic, biomimetic 2-methacryloyloxyethyl phosphorylcholine (MPC) incorporating antibacterial AgBF(4) by inverse miniemulsion is described. The prepared hybrid colloids were designed to provide both antibacterial and antifouling properties for the formation of interesting, multifunctional films. The obtained particles had sizes in the range of 130-160 nm with two different weight ratios of MPC to HEMA (1:10 and 2:5) and AgBF(4) contents between 0% and 15%. The silver salt takes on the role of the lipophobe in stabilizing the miniemulsion droplets against Ostwald ripening and is reduced after polymerization to Ag nanoparticles by gaseous hydrazine. Subsequently, the hybrid particles are transformed into smooth and stable films with thicknesses between 145 and 225 nm by simple drop casting and solvent annealing. The dispersions and films were thoroughly characterized by DLS, TEM, SEM, EDX, TGA, UV-vis spectroscopy, ICP-OES, XRD, AFM, and contact angle measurements. After immersion into water, the films did not show detectable leakage of silver, so they could be employed as dual-functional antifouling and antibacterial coatings.     

内部结构不对称磁性复合微球的制备及其影响因素探究

内部结构不对称复合微球是指无机粒子在复合微球内部呈现规律性、不对称分布的一类微球.采用细乳液聚合的方法一步合成了平均粒径0.8μm、磁含量为46.67%、比饱和磁化强度为23.20 emu/g的内部结构不对称PSt/Fe3O4磁性复合微球.详细考察了Fe3O4纳米粒子表面修饰剂含量、乳化剂、助乳化剂、超分散剂、细乳化时间等因素对于复合微球形貌的影响,探讨了内部结构不对称复合微球的形成机理.同时通过TEM(透射电子显微镜),FTIR(红外光谱),VSM(振动样品磁强计),TG(热失重分析)以及激光粒度仪等表征手段对微球内部形貌、磁化强度及粒径等进行了表征,确定Fe3O4纳米粒子表面性质是微球呈现内部结构不对称的决定性因素.     

Facile preparation method of SiO2/PS/TiO2 multilayer core-shell hybrid microspheres

Organic-inorganic hybrid particles have many potential applications, but almost all of this research was focused on the hybrid particles containing one kind of inorganic nanoparticles. This paper presented a facile preparation method for SiO2/PS/TiO2 multilayer core-shell hybrid microspheres. In this approach, positively charged SiO2/PS core-shell hybrid particles were first synthesized by miniemulsion polymerization using cationic initiator and emulsifier. These positively charged SiO2/PS hybrid particles were mixed with tetra-n-butyl titanate for sol-gel reaction to directly form SiO2/PS/TiO2 multilayer core-shell hybrid microspheres. Some influencing parameters such as surfactant concentration, tetra-n-butyl titanate amount, and glacial acetic acid amount were investigated. TEM, TGA, and EDX analyses indicated that titania layers were successfully coated onto the surfaces of hybrid microspheres.     

pH值和前驱体用量对核壳结构PSt/SiO2复合微球结构形态的影响

首先通过无皂乳液聚合法制得表面含羧基、粒径为360 nm的单分散聚苯乙烯(PSt)种子乳液,并在EtOH/H2O混合介质中用γ-氨丙基三乙氧基硅烷(KH-550)对其进行改性,制得表面含有活性硅乙氧基并带有正电荷的改性PSt乳胶粒,然后再加入原硅酸乙酯(TEOS)进行共水解与共缩聚反应,制备出了核壳结构PSt/SiO2...     

种子表面改性法制备核壳结构PSt/SiO_2复合微球

首先采用无皂乳液聚合法合成了表面带负电荷、粒径为360nm的单分散聚苯乙烯(PSt)种子乳液,并以EtOH/H2O混合物为分散介质,利用γ-氨丙基三乙氧基硅烷(KH-550)在25℃下对PSt微球表面进行改性,得到了表面硅烷化并带有正电荷的改性PSt种子乳液,然后在碱性条件下加入原硅酸乙酯(TEOS)使其和微球进行共水解与共缩聚,制备出了核壳结构PSt/SiO2复合微球,并利用电镜对复合微球的结构形态进行了表征.研究表明,PSt种子乳液改性时体系的zeta电位随着KH-550用量的增加而升高,当KH-550用量为PSt种子重量的1/3时,体系的zeta电位从原来的-34.5mV升高到了38mV,达到对PSt微球表面改性的最佳值;在制备PSt/SiO2复合微球时,TEOS水解缩聚形成的SiO2包覆到改性微球上的量随着反应时间的延长而增加,反应24h时达到97.9%的最大值;随介质中水含量的增加,吸附到复合微球表面上的SiO2纳米颗粒逐渐减少,复合微球表面逐渐变得光滑,当EtOH/H2O质量比降低到60/28.5时,得到结构均一、壳层厚度为35nm的核壳结构PSt/SiO2复合微球。     

Characterization and photocatalytic properties of silver and silver chloride doped TiO2 hollow nanoparticles

Using polystyrene（PSt） particles as template,PSt/TiO₂ composite particles with AgCl incorporation were prepared through hydrolysis of tetrabutyl titanate in the presence of AgNO₃ and NaCl.AgCl doped TiO₂ hollow particles were successfully prepared with the PSt/TiO₂ composite microspheres pretreated at 180℃followed by calcination.The morphology of PSt/TiO₂ particles and the crystal structures of the AgCl doped TiO₂ hollow particles were characterized.The photocatalytic activity of the doped TiO₂ hollow particles in degradation of Rhodamine B was tested under UV and visible lights and compared to that with Ag doped TiO₂ particles.The results showed that TiO₂ hollow particles,either doped with Ag or AgCl,demonstrated higher photocatalytic activity than the pure TiO₂ particles.This enhancement in photocatalytic activity was more significant with AgCl doped TiO₂ than that with Ag doped,and more distinct when the degradation was done under visible light than that under LTV light.     

Synthesis of raspberry‐like silica/polystyrene/silica multilayer hybrid particles via miniemulsion polymerization

Organic–inorganic hybrid particles have many potential applications, but almost all research has been focused on hybrid particles with one kind of inorganic nanoparticle. This article presents a novel and facile preparation approach for raspberry‐like silica/polystyrene/silica multilayer hybrid particles via miniemulsion polymerization. In this method, larger, surface‐modified silica particles are first dispersed into monomer droplets to form a miniemulsion, and then raspberry‐like silica/polystyrene/silica multilayer hybrid particles are directly obtained when miniemulsion polymerization is performed in the presence of smaller, unmodified silica particles with 4‐vinylpyridine as an auxiliary monomer. Influential parameters such as the amount of 4‐vinylpyridine, the surfactant concentration, and the pH value of the system have been investigated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1028–1037, 2007     

Mathematical modeling of seeded miniemulsion copolymerization for oil-soluble initiator

A mathematical model of seeded miniemulsion copolymerization of styrene-methyl methacrylate for oil-soluble initiator is presented. The mathematical model includes the mass transfer, from the miniemulsion droplets to the polymer particles, by both molecular diffusion and collision between miniemulsion droplets and the polymer particles. The mathematical model also includes the calculation of both the distribution of partices with i radicals and the average number of radicals per particle in the miniemulsion copolymerization using oil-soluble initator. Studies were carried out on the mass transfer coefficients of monomers across the interface between the miniemulsion droplet and the aqueous phase, hexadecane concentration in the miniemulsion droplets, the miniemulsion droplet sizes, and the collision between miniemulsion droplets. The results indicated that the copolymerization of styrene-methyl methacrylate was not a mass transfer controlled process. The mass transfer by collision between miniemulsion droplets and polymer particles plays an important role and was included in the model in order to predict the experimental data of seeded miniemulsion copolymerization.     

团聚纳米SiO_2在苯乙烯乳液聚合过程中的再分散过程及机理

用二氧化硅 (SiO2 )存在下的乳液聚合法制备了聚苯乙烯 (PSt) 纳米SiO2 复合材料 ,研究了苯乙烯(St)乳液聚合过程中团聚纳米SiO2 的解离与再分散过程及分散的机理 .发现商品纳米SiO2 粒子以团聚体形式存在 ,团聚体大小远超出纳米级范围 .随聚合时间的延长 ,St的转化率逐渐增加 ,而PSt SiO2 复合微胶囊的粒径逐渐减小 ,反应 12 0min后 ,转化率和复合微胶囊粒子的粒径趋于稳定 .透射电镜 (TEM)也显示PSt SiO2 复合微胶囊粒子具有海岛结构 ,而SiO2 粒子的粒径在纳米范围内 ,表明在乳液聚合过程中SiO2 团聚体被逐渐解离 ,并重新分散到纳米尺度 .红外光谱研究发现 ,在乳液聚合过程中 ,除生成PSt均聚物外 ,还在纳米SiO2 表面生成了PSt接枝共聚物 ,改善了无机纳米粒子与聚合物之间的界面相容性 .聚合过程中的反应热和剪切搅拌是团聚体被解离和重新分散的主要原因 ,而生成的聚合物起到隔离作用     

Miniemulsion polymerization: An approach to control copolymer composition

The copolymerization of vinyl acetate (VAc) and vinyl 2-ethylhexanoate (V2EH) via miniemulsion polymerization is being investigated with the goal of better copolymer composition control. The reaction kinetics and final particle sizes were compared for homopolymerizations and copolymerizations of the two monomers. Enhanced polymerization rates were seen for the miniemulsion polymerizations over their conventional counterparts despite a decreased number of particles. This was attributed to the influence of the reactive surfactant sodium dodecyl allyl sulfosuccinate and low water solubility of the V2EH monomer. Increased nucleation of miniemulsion droplets was sought by incorporation of small amounts of polymer into the droplets. This was first shown to be effective for styrene miniemulsion polymerizations and was subsequently successfully extended to the VAc/V2EH system     

Stabilization of miniemulsion droplets by cerium oxide nanoparticles: a step toward the elaboration of armored composite latexes

Stable methyl methacrylate (MMA) miniemulsions were successfully prepared using for the first time cerium oxide (CeO(2)) nanoparticles as solid stabilizers in the absence of any molecular surfactant. The interaction between MMA droplets and CeO(2) nanoparticles was induced by the use of methacrylic acid (MAA) as a comonomer. Both MAA and CeO(2) contents played a key role on the diameter and the stability of the droplets formed during the emulsification step. Cryo-transmission electron microscopy (TEM) images of the suspensions formed with 35 wt % of CeO(2) showed the presence of polydisperse 50-150 nm spherical droplets. More surprisingly, some nonspherical (likely discoidal) objects that could be the result of the sonication step were also observed. The subsequent polymerization of these Pickering miniemulsion droplets led to the formation of composite PMMA latex particles armored with CeO(2). In all cases, the conversion was limited to ca. 85%, concomitant with a loss of stability of the latex for CeO(2) contents lower than 35 wt %. This stability issues were likely related to the screening of the cationic charges present on CeO(2) nanoparticles upon polymerization. TEM images showed mostly spherical particles with a diameter ranging from 100 to 400 nm and homogeneously covered with CeO(2). Besides, for particles typically larger than 200 nm, a buckled morphology was observed supporting the presence of residual monomer at the end of the polymerization and consistent with the limited conversion. The versatility of these systems was further demonstrated using 35 wt % of CeO(2) and replacing MMA by n-butyl acrylate (BA) either alone or in combination with MMA. Stable monomer emulsions were always obtained, with the droplet size increasing with the hydrophobicity of the oil phase, pointing out the key influence of the wettability of the solid stabilizer. The polymerization of Pickering miniemulsion stabilized by CeO(2) nanoparticles proved to be an efficient strategy to form armored composite latex particles which may find applications in coating technology.     

共沉淀法制备Ag/AgCl-TiO2空心复合纳米微球及其光催化性能

通过甲基丙烯酸与苯乙烯聚合制备了表面负电性的聚苯乙烯(PSt)纳米乳胶粒. 在乙醇与水的混合溶剂中, 用硅烷偶联剂乙烯基三甲氧基硅烷对其进行表面改性后加入钛酸四丁酯、 氯化钠和硝酸银, 以PSt乳胶粒为模板采用共沉淀法制备了PSt-AgCl-TiO₂复合微球. 在180 ℃对其进行液相预处理及煅烧去除PSt模板后制备了Ag/AgCl-TiO₂空心复合粒子. 对各阶段产物的形貌、 晶体结构和比表面积等进行了表征. 结果表明, 所得产物为Ag/AgCl与锐钛矿型TiO₂复合的空心粒子, 其比表面远大于商品TiO₂(P25). 考察了Ag/AgCl-TiO₂复合粒子在紫外光与可见光下对罗丹明B(RhB)降解的催化活性. 结果表明, 在紫外光下n(Ag)/n(Ti)=0.1%的Ag/AgCl-TiO₂复合粒子活性最高, 30 min时对RhB的降解率比不含Ag/AgCl的TiO₂空心微球提高了13%; 虽然Ag/AgCl-TiO₂在可见光下的催化活性远比紫外光下低, 但与纯TiO₂空心纳米微球相比其催化活性仍明显增强. n(Ag)/n(Ti)=2.0%的Ag/AgCl-TiO₂复合粒子催化活性最高, 120 min时对RhB的降解率比不含Ag/AgCl的TiO₂空心微球提高了38%.     

Evolution of particle morphology during the synthesis of hybrid acrylic/CeO2 nanocomposites by miniemulsion polymerization

The evolution of the morphology of an acrylic/CeO₂ hybrid latex synthesized by a two step seeded semibatch emulsion polymerization process was investigated. The seed was produced by batch miniemulsion polymerization and in the second step a neat monomer preemulsion was fed to the seed to increase the solids content and encapsulate the inorganic material. The morphology of the hybrid miniemulsion droplets, the seed and the final latex was analyzed by TEM. The morphologies achieved could be explained by theoretical equilibrium morphology maps based on the interfacial tensions of the monomeric, polymeric, inorganic and aqueous phases. © 2014 Wiley Periodicals, Inc. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 792–799     

Dispersion of SiO2-based nanocomposites with high performance liquid chromatography

Core-shell structured Ag/SiO2 nanocomposite has been synthesized by a cyclohexane/Igepal/water reverse micelle system. The spherical nanocomposite particles were washed and concentrated with high performance liquid chromatography (HPLC) to remove the surfactant added during synthesis. Spherical SiO2 micrometer-scale particles were packed in the HPLC column as a stationary phase for the washing and dispersing of Ag/SiO2 nanocomposite particles. Surface modification of Ag/SiO2 nanocomposite particles and SiO2 microspheres with silane coupling agent enhanced the surface charge of the particles and improved the efficiency of washing with HPLC. Well-dispersed Ag/SiO2 stable suspensions were successfully attained in ethanol/water mixed solvents after HPLC washing. The state of dispersion for the Ag/SiO2 nanocomposite suspension was systematically assessed using dynamic light scattering (DLS) and transmission electron microscope (TEM) and spin coat/atomic force microscope (AFM) analyses. The mechanism of the enabling HPLC washing protocol for SiO2-based nanoparticles is discussed.     

Preparation of monodisperse SiO2 nanoparticles by membrane emulsification using ideally ordered anodic porous alumina

Monodisperse SiO2 particles of nanometer dimensions were fabricated by membrane emulsification using ideally ordered anodic porous alumina. For the preparation of monodisperse emulsion droplets, the dispersed phase was pressed through a porous alumina membrane into the continuous phase. After solidification treatment of the emulsion droplets, prepared spherical SiO2 nanoparticles with uniform sizes were obtained. From scanning electron microscope observation of the obtained particles, it was confirmed that the size distribution of SiO2 nanoparticles is relatively narrow.     

Comparative study of monomer droplet nucleation in the seeded batch and semibatch miniemulsion polymerisation of styrene

Monomer droplet nucleation in the seeded miniemulsion polymerisation of styrene under monomer-flooded and monomer-starved conditions was studied. The miniemulsion feeds were added to the reactor either batchwise or semibatchwise. The droplets preserved longer under flooded conditions. As a result, the batch operation led to a larger number of particles (N_p) than the semibatch operation. For the miniemulsion droplets containing predissolved polymer, the final N_p was independent of the way that the feed was added to the reactor and was equivalent to the number of monomer droplets in the original miniemulsion feed. The size distribution of the final latexes, however, was influenced by the operation type. For the batch operation, the rate of polymerisation (R_p) with the miniemulsion feeds was higher than that with the conventional monomer emulsion feed because of the monomer droplet nucleation. But for the semibatch operation, the opposite was true because of R_p controlled by the rate of monomer diffusion from rather stable miniemulsion droplets to the growing polymer particles.     

Morphology of PU/PMMA hybrid particles from miniemulsion polymerization: Thermodynamic considerations

The morphology of PU/PMMA hybrid particles prepared by miniemulsion polymerization was predicted through the consideration of their Gibbs free energy changes. Five morphological states of PU/PMMA hybrid particles were proposed and their Gibbs free energy changes were calculated. Before the formation of hybrid particles, the initial state included a monomer mixture of PU prepolymer, MMA, a chain extender, TMP, and an initiator, which was in droplets suspended in water containing SDS. Two assumptions were made. First, the densities of all states were the same. Secondly, secondary nucleation of particles was negligible. Thus the size of initial droplet and final particle was unchanged through miniemulsion polymerization. The interfacial tensions were measured by a pendant drop method and were used for calculation. The preferred morphology of PU/PMMA hybrid particle had the minimum value of ΔG_phase. Different NCO/OH ratios of PU and initiators of MMA were used to study the morphological change of PU/PMMA hybrid particles. When BD was used as the chain extender of PU, the hybrid particles showed the PU‐rich phase as the shell and PMMA‐rich as the core. When incorporating bisphenol A into PU polymer, the homogeneous structure of hybrid particle was preferred. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3359–3369, 2007     

Miniemulsion copolymerization of styrene–methyl methacrylate

Miniemulsion copolymerization of 50 : 50 weight fraction of styrene–methyl methacrylate monomer, using hexadecane as the cosurfactant, was carried out in both unseeded and seeded polymerizations. Effects of the hexadecane concentration and the ultrasonification time on the conversion–time curves and particle size of the final latex were investigated for unseeded polymerization. The kinetic and particle size distribution results showed that an increase in hexadecane concentration and ultrasonification time cause faster polymerization rate and smaller particle size. The mechanism of mass transport from miniemulsion droplets to polymer particles was also investigated for seeded polymerization. For this purpose a monomer miniemulsion was mixed with a fraction of a previously prepared miniemulsion latex particles prior to initiation of polymerization, using residual oil-soluble initiator in the seed latex. The concentration of hexadecane and a water-insoluble inhibitor (2,5 di-tert-butyl hydroquinone) in the miniemulsions were the main variables. Seeded polymerizations were also carried out in the presence of miniemulsion droplets containing a water-insoluble inhibitor and water-soluble initiator. The inhibitor concentration and the agitation speed during the course of polymerization were the experimental variables. The kinetic and particle size results from these seeded experiments suggested that collision between miniemulsion droplets and polymer particles may play a major role in the transport of highly water-insoluble compounds.     

Synthesis of SiO2/polystyrene nanocomposite particles via miniemulsion polymerization

The SiO(2)/polystyrene nanocomposite particles were synthesized through miniemulsion polymerization by using sodium lauryl sulfate surfactant (SLS), hexadecane costabilizer in the presence of silica particles coated with methacryloxy(propyl)trimethoxysilane. Core-shell or other interesting morphology composite particles were obtained depending on the size of the silica particles and the surfactant concentration employed. By adjusting these parameters, it was possible to control the size and morphology of the composite particles.