Anchoring of polyacrylate onto silica and formation of polyacrylate/silica nanocomposite particles via in situ emulsion polymerization

Polyacrylate/silica nanocomposite latex particles were prepared by in situ emulsion polymerization of acrylate monomers initiated by 2,2′-azobis(2-amidinopropane)dihydrochloride (AIBA) adsorbed by silica nanoparticles. The anchoring of polyacrylate (ACR) onto silica nanoparticles was achieved through the physical absorption and chemical grafting reaction. The elution and HF etching experiments showed that most silica nanoparticles were encapsulated by ACR to form the raspberry-like ACR/silica nanocomposite latex particles. The silica nanoparticles with a greater grafting degree of ACR tended to locate in the bulk of the polymer, and the silica particle with a lower grafting degree would not be combined with polymer latex particles and always remained in water phase. The formation of the final ACR/silica nanocomposite latex particles included the anchoring of ACR onto silica primary particles, aggregation of silica primary particles to form the silica-containing latex particles, and the growth of latex particles.     

Kinetics of vinyl acetate emulsion polymerization

The emulsion polymerization of vinyl acetate has generally been considered a special type of reaction that is not covered by the Smith-Ewart theory. Although the number of particles depends on coalescence rates and can not be predicted by this theory, the polymerization rate data are consistent with the general concepts of Smith and Ewart, including reaction primarily inside swollen polymer particles, escape of radicals from particles, and termination of chains inside the particles. Allowing for rapid exchange of radicals following chain transfer leads to a simple equation which fits much of the published data for cases of both very low and very high values of n , the average number of radicals per particle.      

Synthesis of narrowly distributed polystyrene-encapsulated silica nanoparticles via emulsion polymerization

Polystyrene (PS)-encapsulated silica nanoparticles were successfully synthesized by conventional emulsion polymerization for solving the aggregation matter of nanoscaled silica. The grafting coupling agents and PS on the silica surface were detected by Fourier Transform Infrared (FTIR) spectroscopy. The influence of silica and monomer to water ratios and initiator concentration on particle size distribution of the nanocomposite latex was investigated. The particle size distribution firstly narrowed and then broadened with the increase of silica and monomer to water ratios and initiator concentration. The narrow distribution could be controlled in an appropriate silica and monomer to water ratio and an initiator concentration of 1/15 and 2 wt%, respectively. From the evaluation of transmission electron microscopy (TEM) micrographs and dynamic light scattering (DLS) measurement, it was proved that the nanocomposite latex did not have all sphere-like shape, but contained tiny amounts of irregular bodies. The formation mechanism of PS-encapsulated silica nanoparticles was also discussed.     

Emulsion polymerization of ethylene from mesoporous silica nanoparticles with vinyl functionalized monolayers

Emulsion polymerization of ethylene from vinyl functionalized mesoporous silica nanoparticles (V‐MSNs) was reported. V‐MSNs were synthesized via deposition of vinyl monolayers on the pore walls, and the relative surface coverage of the vinyl monolayers was 74%. A fluorinated P‐O‐chelated nickel catalyst coordinated to the vinyl groups. These V‐MSNs hosting catalysts were full dispersed in water assisted by ultrasonic processor in the presence of surfactants. After addition of ethylene, polyethylene (PE) chains grew from the pores of V‐MSNs, formation of stable nanocomposite latices with solid content up to 17.3%. Our method made V‐MSNs well‐dispersed in the PE matrix. Especially, because of a strong interaction between PE and nanoparticles, a stable V‐MSNs core/PE shell structure was formed upon thermal treatment above melting temperature of the PE. Samples were analyzed by a number of techniques including TEM, N₂ adsorption‐desorption, FTIR, and solid state ²⁹Si NMR, DLS, ¹H NMR, GPC, and DSC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1393–1402, 2009     

Preparation and characterization of polymer/silica nanocomposites via double in situ miniemulsion polymerization

Polymer/SiO₂ nanocomposite microspheres were prepared by double in situ miniemulsion polymerization in the presence of methyl methacrylate, butyl acrylate, γ‐methacryloxy(propyl) trimethoxysilane, and tetraethoxysilane (TEOS). By taking full advantage of phase separation between the growing polymer particles and TEOS, inorganic/polymer microspheres were fabricated successfully in a one‐step process with the formation of SiO₂ particles and the polymerization of organic monomers taking place simultaneously. The morphology of nanocomposite microspheres and the microstructure, mechanical properties, thermal properties, and optical properties of the nanocomposite films were characterized and discussed. The results showed that hybrid microspheres had a raspberry‐like structure with silica nanoparticles on the shells of polymer. The silica particles of about 20 nm were highly dispersed within the nanocomposite films without aggregations. The transmittance of nanocomposite film was comparable to that of the copolymer film at around 70–80% from 400 to 800 nm. The mechanical properties and the fire‐retardant behavior of the polymer matrix were improved by the incorporation of silica nanoparticles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3128–3134, 2010     

All-acrylic film-forming colloidal polymer/silica nanocomposite particles prepared by aqueous emulsion polymerization

The efficient synthesis of all-acrylic, film-forming, core-shell colloidal nanocomposite particles via in situ aqueous emulsion copolymerization of methyl methacrylate with n-butyl acrylate in the presence of a glycerol-functionalized ultrafine silica sol using a cationic azo initiator at 60 °C is reported. It is shown that relatively monodisperse nanocomposite particles can be produced with typical mean weight-average diameters of 140-330 nm and silica contents of up to 39 wt %. The importance of surface functionalization of the silica sol is highlighted, and it is demonstrated that systematic variation of parameters such as the initial silica sol concentration and initiator concentration affect both the mean particle diameter and the silica aggregation efficiency. The nanocomposite morphology comprises a copolymer core and a particulate silica shell, as determined by aqueous electrophoresis, X-ray photoelectron spectroscopy, and electron microscopy. Moreover, it is shown that films cast from n-butyl acrylate-rich copolymer/silica nanocomposite dispersions are significantly more transparent than those prepared from the poly(styrene-co-n-butyl acrylate)/silica nanocomposite particles reported previously. In the case of the aqueous emulsion homopolymerization of methyl methacrylate in the presence of ultrafine silica, a particle formation mechanism is proposed to account for the various experimental observations made when periodically sampling such nanocomposite syntheses at intermediate comonomer conversions.     

Preparation and characterization of surfactant-free polystyrene/layered double hydroxide exfoliated nanocomposite via soap-free emulsion polymerization

The soap-free emulsion polymerization has been applied for preparing the surfactant-free polystyrene/layered double hydroxide exfoliated nanocomposite. The XRD and TEM determinations have been used to monitor the changes of interlayer spacing and morphology during polymerization. The results show that the obtained nanocomposite has the homogeneous structure of polymeric and inorganic components. Due to the absence of organic surfactant, the PS/LDH nanocomposite shows a remarked improvement on the onset decomposition temperature compared with virgin PS.     

Preparation and properties of poly(vinyl alcohol)/silica nanocomposites derived from copolymerization of vinyl silica nanoparticles and vinyl acetate

Nanocomposites of poly(vinyl alcohol)/silica nanoparticles (PVA-SNs) were prepared by in-situ radical copolymerization of vinyl silica nanoparticles functionalized by vinyltriethoxysilane (VTEOS) and vinyl acetate with benzoyl peroxide (BPO, i.e., initiator), subsequently saponified via direct hydrolysis with NaOH solution. The resulting vinyl silica nanoparticles, PVA-SNs were characterized by means of fourier transformation spectroscopy (FTIR), transmission electron microscopy (TEM) and the elemental analysis method. Effects of silica nanoparticles on viscosity and alcoholysis of PVA-SNs were studied by a ubbelohode capillary viscometer and the back titration method. The morphological structure of PVA-SN films was investigated by scanning electron microscopy (SEM). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile test were used to determine the thermal and mechanical properties of PVA-SN films. The results indicated that the content of vinyl groups on the surface of the vinyl silica nanoparticles was up to 3.02 mmol/g and vinyl silica nanoparticles had been successfully copolymerized with vinyl acetate. Furthermore, compared to pure PVA, silica nanoparticles bonded with polymer matrix in a low concentration affected the viscosity and alcoholysis of the PVA-SNs materials. At the same time, it resulted in the improvement of the thermal and mechanical properties of the PVA-SN materials due to a strong interaction between silica nanoparticles and the polymer matrix via a covalent bond. It could be found that the optical clarity of the membrane was changed through UV-Vis absorption spectrum due to the introduction of silica nanoparticles.     

乳液聚合法制备纳米金/聚苯乙烯复合粒子

以氯金酸为前驱体,十二烷基硫醇和硼氢化钠分别作为稳定剂和还原剂,采用相转移法制备了单分散的金纳米粒子.将金纳米粒子通过乳液聚合的方法制备了纳米金/聚苯乙烯复合粒子.通过紫外-可见吸收光谱(UV-Vis)研究了纳米金和纳米金/聚苯乙烯复合粒子的光吸收特性,使用傅立叶变换红外光谱(FT-IR)、X射线衍射(XRD)、透射电子显微镜(TEM)和动态光散射(DLS)对产物的组成、晶体结构、形貌、以及粒径进行了表征.结果表明,复合粒子为粒径分布较窄的球形,其中的金纳米粒子为面心立方结构.热失重分析(TGA)说明制备的纳米金/聚苯乙烯复合粒子具有很好的热稳定性.     

Synthesis and characterization of silica/poly (methyl methacrylate) nanocomposite latex particles through emulsion polymerization using a cationic azo initiator

Following a previous work (J. L. Luna-Xavier et al., Colloid Polym. Sci.279, 947 (2001)), silica-poly (methyl methacrylate) (PMMA) nanocomposite latex particles have been synthesized in emulsion polymerization using a cationic initiator, 2,2'-azobis (isobutyramidine) dihydrochloride (AIBA), and a nonionic polyoxyethylenic surfactant (NP30). Silica beads with diameters of 68, 230, and 340 nm, respectively, were used as the seed. Coating of the silica particles with PMMA was taking place in situ during polymerization, resulting in the formation of colloidal nanocomposites with a raspberry-like or a core-shell morphology, depending on the size and nature of the silica beads. The amount of surface polymer was quantified by means of ultracentrifugation and thermogravimetric analysis as extensively described in the first article of the series (see above reference). The influence of some determinant parameters such as the pH of the suspension, the initiator, silica, monomer, or surfactant concentration on the amount of coating polymer and on the efficiency of the coating reaction was investigated in details and discussed in light of the physicochemical properties of the seed mineral. Electrostatic attraction between the positive end groups of the macromolecules and the inorganic surface proved to be the driving force of the polymer assembly on the seed surface at high pH, while polymerization in adsorbed surfactant bilayers (so-called admicellar polymerization) appeared to be the predominant mechanism of coating at lower pH. Optimal conditions have been found to reach high encapsulation efficiencies and to obtain a regular polymer layer around silica.     

Kinetic analysis of seeded emulsion polymerization of vinyl acetate

Particle number and size data from a series of seeded, emulsifier-free, vinyl acetate emulsion polymerization experiments have been analyzed with the aid of polymerization and particle growth models. A secondary population of particles, with a significantly greater number concentration than the seed, was nucleated in all experiments. The two populations (seed and new) had rather narrow size distributions and large diameters. Hence the reactions were in the area normally associated with Smith–Ewart Case III kinetics. Water-phase termination reactions can be important in this reaction region but radical desorption from such large particles does not significantly influence the kinetics. The results of the analysis were used to evaluate the magnitude of water-phase termination; to estimate radical capture coefficients; and to evaluate competitive particle growth.     

Preparation and characterization of a novel nanocomposite: silver nanoparticles decorated cerasome

In this study, a novel artificial hybrid vesicle, nano silver particles decorated cerasome were fabricated through sol–gel and self-assemble methods as well as in situ reduction. Samples were characterized in terms of hydrodynamic size and surface morphology via dynamic light scattering as well as scanning and transmission electron microscopies. Analysis through energy dispersive X-ray spectrometer proved the existence of silver particles. Due to the high morphological stability of cerasome, Silver nanoparticles with a size of about 5–10 nm can be deposited on the surface without any stabilizers. The UV spectra revealed a single symmetric extinction peak at 406 nm, confirming the spherical shape of the synthesized silver nanoparticles. Several reducing agents were screened before confirming sodium borohydride (NaBH₄). Comparison of different NaBH₄/lipid ratios (K_{NaBH4/cerasome-forming lipid}) was then carried out in order to ascertain its effect. Investigation of the stability of this hybrid vesicles was carried out, indicating that it can be stored at 4 °C for at least 3 months without any morphological change. Results demonstrated that this hybrid vesicle has excellent morphological stability, which impart it significant potential for various applications such as being an antibacterial material and a radio sensitization agent.     

Role of electrolytes in the preparation of nanoparticles via the emulsion polymerization of vinyl pivalate

By controlling both the kind of ion and the ionic strength of electrolytes in an emulsion polymerization system of vinyl pivalate containing about 1% sodium lauryl sulfate as a surfactant, nanoparticles of polyvinylpivalate having a diameter of about 25 nm were successfully prepared. The use of high concentrations of lithium chloride and lithium sulfate (1.0 mol L⁻¹) prevented the nanoparticles from aggregating and produced nanoparticles sizes of 25–50 nm. Ammonium acetate and sodium acetate, on the other hand, accelerated the aggregate of the nanoparticles. These phenomena were examined in detail and found to be similar to the Hofmeister phenomena and the combination rule proposed by Craig et al.     

Seeded polymerization of vinyl acetate using monodisperse poly(vinyl acetate) latex particles

The seeded polymerizations of vinyl acetate, using monodisperse poly(vinyl acetate) latex particles prepared in the absence of emulsifiers with potassium persulfate, have been investigated at 70°C with potassium persulfate as an initiator. New small particles were formed in the system containing a small amount of seed particles, but were not observed in the system containing a large amount of seed particles. The size of the secondary particles increased, and their number decreased, with an increase in the seed particle number. The minimum diameter of PVAc particles, which are stabilized by the sulfate ion groups bound at the end of polymer chains during polymerization, was determined to be 0.12 μm diameter from the limiting total surface area of seed particles which prevented further secondary nucleation. The minimum diameter of the particles increased as the speed of the stirrer increased. The new small particle number calculated using this value agreed well with that formed in the seeded polymerization.     

Preparation of SiO2/PMMA composite particles via conventional emulsion polymerization

A series of SiO₂/PMMA composite particles with different morphologies were prepared by conventional emulsion polymerization by the aid of acid–base interaction between the silanol groups of unmodified silica particles and the amino groups of 4‐vinylpyridine. In this approach, no surface treatment for nanosilica particles was required. The morphologies of composite particles, for example, multicore–shell, raspberry‐like, and conventional core–shell, could be controlled by modulating emulsifier content, monomer/silica ratio, silica size, and monomer feed method. The possible particle formation mechanisms were discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3807–3816, 2006     

RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate)

The preparation of poly(vinyl acetate) with well-controlled structure has received a great deal of interest in recent years because of a large number of developments in living radical polymerization techniques. Among these techniques, the use of reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization has been employed for the controlled polymerization of vinyl acetate due to the high susceptibility of this monomer towards chain transfer reactions. Here, a novel water-soluble N,N-dialkyl dithiocarbamate RAFT agent has been prepared and employed in the emulsion polymerization of vinyl acetate. The kinetic results reveal that the polymerization nucleation mechanism changes from homogeneous to micellar and RAFT-generated radicals can change the kinetic behavior from conventional emulsion polymerization to living radical polymerization. At higher concentrations of the modified RAFT agent, as a result of an aqueous phase reaction between RAFT and sulfate radicals, relatively more hydrophobic radicals are generated, which favors entry and propagation into micelles swollen with monomer. This observation was determined from the investigation of the polymerization rate and measurements of the average particle diameter and the number of particles per liter of the aqueous phase. Molecular weight analysis also demonstrated the participation of the RAFT agent in the polymerization in such a way as to restrict chain transfer reactions. This was determined by examining the evolution of polymer chain length and attaining higher molecular weights, even up to 50?% greater than the samples obtained from the conventional emulsion polymerization of vinyl acetate in the absence of the synthesized modified RAFT agent.     

纳米金-钛酸纳米管复合材料的合成与表征

以氯金酸和钛酸钠米管(NTA)为原料,柠檬酸三钠为稳定剂,硼氢化钠为还原剂,于室温条件下合成了一种金纳米颗粒-钛酸纳米管(GNPs-NTA)复合纳米材料;利用红外光谱仪、透射电镜、X射线粉末衍射仪等分析了产物的化学键合特征、微结构及相组成,并考察了产物对辣根过氧化酶(HRP)结构和生理活性的影响.结果表明,合成的纳米金颗粒粒径(平均5.3nm)分布窄,且均匀分布于钛酸纳米管表面.此外,HRP与GNPs-NTA复合纳米材料充分振荡混合后仍能保持其二级结构不变,有利于保持其生理活性.     

Synthesis and characterization of exfoliated polystyrene/ZnAl layered double hydroxide nanocomposite via emulsion polymerization

Exfoliated polystyrene (PS)/ZnAl layered double hydroxide (LDH) nanocomposites have been synthesized via emulsion polymerization in the presence of N-lauroyl-glutamate surfactants and long-chain n-hexadecane. The samples were characterized using elemental analysis, Fourier transform infrared (FTIR) spectrum, X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The XRD and TEM results demonstrate that the exfoliated ZnAl-LDH layers of 50-70 nm width and about 1 nm thickness were well dispersed at molecular level in the PS matrix. And the completely exfoliated PS/LDH nanocomposites can be obtained even at the 10 wt% LDH loading. When the 50% weight loss was selected as a comparison point, the decomposition temperature of exfoliated PS/LDH sample with 5 wt% LDH was ca. 28 degrees C higher than that of pure PS.     

Gas permeation properties of ethylene vinyl acetate–silica nanocomposite membranes

The effect of silica nanoparticles on the gas separation properties of ethylene vinyl acetate (EVA) copolymer containing 28% vinyl acetate has been investigated. The EVA and hybrid EVA–silica membranes were prepared via thermal phase inversion method. Silica nanoparticles prepared by hydrolysis of tetraethylorthosilicate (TEOS), through the sol–gel mechanism. The prepared membranes were characterized using FT-IR, SEM, DSC and XRD methods. FT-IR and SEM results indicated the nanoscale dispersion of silica particles in polymer matrix. As confirmed by XRD and DSC analyses, increasing the silica content enhances the amorphous regions significantly. Gas permeation of EVA–silica nanocomposite membranes with silica contents of 5, 6 and 10 wt.% was studied for N₂, O₂, CO₂ and CH₄ single gases at pressures of 4, 6 and 8 bar. The obtained results suggest a significant increase in permeability of all gases and an increase in CO₂/N₂ and CO₂/CH₄ gases selectivities upon increasing the silica content. The possible reasons for such behavior were stated and discussed. The pressure dependence of the gas permeabilities of the membranes was also investigated.