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1.
Amphiphilic polymeric particles with hydrophobic cores and hydrophilic shells were prepared via living radical emulsion polymerization of styrene using a water‐soluble poly(acrylamide)‐based macro‐RAFT agent in aqueous solution in the absence of any surfactants. Firstly, the homopolymerization of acrylamide (AM) was carried out in aqueous phase by reversible addition‐fragmentation chain transfer radical polymerization (RAFT) using a trithiocarbonate as a chain transfer agent. Then the PAM‐based macro‐RAFT agent has been used as a water‐soluble macromolecular chain transfer agent in the batch emulsion polymerization of Styrene (St) free of surfactants. The RAFT controlled growth of hydrophobic block led to the formation of well‐defined poly(acrylamide)‐copolystyrene amphiphilic copolymer, which was able to work as a polymeric stabilizer (self‐stability). Finally, very stable latex was prepared, having no visible phase separation for several months. FTIR and 1H‐NMR measurements showed that the product was the block copolymer PAM‐co‐PS in the form of stable latex. Atomic force microscope (AFM), transmission electron microscope (TEM), and dynamic light scattering (DLS) studies indicated that the nanoparticles have a narrow particle size distribution and the average particle hydrodynamic radius was kept in the diameter of 58 nm. Core‐shell structure of the copolymer was also recorded by TEM. The mechanism of the self‐stability of polymer particles during the polymerization in the absence of surfactants was studied. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3098–3107, 2008  相似文献   

2.
Magnetic iron oxide nanoparticles synthesized by coprecipitation and thermal decomposition yield largely monodisperse size distributions. The diameters of the coprecipitated particles measured by X‐ray diffraction and transmission electron microscopy are between approximately 9 and 15 nm, whereas the diameters of thermally decomposed particles are in the range of 8 to 10 nm. Coprecipitated particles are indexed as magnetite‐rich and thermally decomposed particles as maghemite‐rich; however, both methods produce a mixture of magnetite and maghemite. Fourier transform IR spectra reveal that the nanoparticles are coated with at least two layers of oleic acid (OA) surfactant. The inner layer is postulated to be chemically adsorbed on the nanoparticle surface whereas the rest of the OA is physically adsorbed, as indicated by carboxyl O? H stretching modes above 3400 cm?1. Differential thermal analysis (DTA) results indicate a double‐stepped weight loss process, the lower‐temperature step of which is assigned to condensation due to physically adsorbed or low‐energy bonded OA moieties. Density functional calculations of Fe–O clusters, the inverse spinel cell, and isolated OA, as well as OA in bidentate linkage with ferrous and ferric atoms, suggest that the higher‐temperature DTA stage could be further broken down into two regions: one in which condensation is due ferrous/ferrous– and/or ferrous/ferric–OA and the other due to condensation from ferrous/ferric– and ferric/ferric–OA complexes. The latter appear to form bonds with the OA carbonyl group of energy up to fivefold that of the bond formed by the ferrous/ferrous pairs. Molecular orbital populations indicate that such increased stability of the ferric/ferric pair is due to the contribution of the low‐lying Fe3+ t2g states into four bonding orbitals between ?0.623 and ?0.410 a.u.  相似文献   

3.
In this work, an iron oxide (Fe3O4)/polystyrene (PS)/poly(N‐isopropylacryl amide‐co‐methacrylic acid) [P(NIPAAM–MAA)] thermosensitive magnetic composite latex was synthesized by the method of two‐stage emulsion polymerization. The Fe3O4 particles were prepared by a traditional coprecipitation method and then surface‐treated with either a PAA oligomer or lauric acid to form a stable ferrofluid. The first stage for the synthesis of the thermosensitive magnetic composite latex was to synthesize PS in the presence of a ferrofluid by emulsion polymerization to form Fe3O4/PS composite latex particles. Following the first stage of reaction, the second stage of polymerization was carried out with N‐isopropylacryl amide and methacrylic acid as monomers and with Fe3O4/PS latex as seeds. The Fe3O4/PS/[P(NIPAAM–MAA)] thermosensitive magnetic particles were thus obtained. The effects of the ferrofluids on the reaction kinetics, morphology, and particle size of the latex were discussed. A reaction mechanism was proposed in accordance with the morphology observation of the latex particles. The thermosensitive property of the thermosensitive magnetic composite latex was also studied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3062–3072, 2007  相似文献   

4.
Crosslinked poly(2‐hydroxyethyl methacrylate)‐based magnetic microspheres were prepared in a simple one‐step procedure by dispersion polymerization in the presence of several kinds of iron oxides. Cellulose acetate butyrate and dibenzoyl peroxide were used as steric stabilizer and polymerization initiator, respectively, and ethylene dimethacrylate was a crosslinking agent. The resulting product was characterized in terms of particle size, particle size distribution, iron(III) content, and magnetic properties. In the presence of needle‐like maghemite in the polymerization mixture and under suitable conditions, magnetic microspheres with relatively narrow size distribution were formed. An increase in the particle size and, at the same time, a decrease in molecular weight of uncrosslinked polymers resulted, as the continuous phase became richer in 2‐methylpropan‐1‐ol. Coercive force of needle‐like maghemite‐containing particles was higher than that of cubic magnetite‐loaded microspheres. Coercive force increased with the decreasing iron content in the particles. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1161–1171, 2000  相似文献   

5.
Glass transition characteristics and mechanical wave attenuation of the neat and filled styrene‐butadiene rubber (SBR) containing 10 wt % of rigid monosize polystyrene particles of various diameters from several hundred microns down to several tens of nanometers were investigated by dynamic mechanical thermal analysis, impedance tube, and ultrasonic spectroscopy. The results showed the matrix damping capacity and the breadth of glass transition increase by reducing the size of rigid particles due to the matrix‐particles interfacial area increase as the major governing parameter. Matrix glass transition broadening toward higher temperatures was attributed to the increased dynamic heterogeneity induced by fillers, whereas the damping capacity increase was assigned to contribution of interfacial friction loss mechanism. The proposed postulation was confirmed based on the calculated temperature distribution of the relaxing matrix volume fraction. Sound wave attenuation by the matrix and PS particles filled systems led to a broad absorption peak for the former and appearance of a secondary absorption peak at lower frequencies for the latter. Intensity of this secondary peak was highest for the system containing PS nanoparticles. Finally, ultrasonic attenuation enhanced by the PS particle size to wavelength ratio increase according to αsca ~ (d/λ)0.38 scaling law and declined by replacing the dense particles with larger hollow PS particles. Comparison of the normalized attenuation of the PS particle filled SBR in various mechanical wave attenuation regimes implied low sensitivity to particle size in vibration, mild differentiation in the sound, and finally severe differentiation in the ultrasound regimes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 82–88, 2010  相似文献   

6.
The functionalization of nanoparticle surfaces is required to improve the dispersion of an inorganic material inside an organic matrix. In this work, polystyrene (PS) brushes were grown on the surface of iron oxide magnetic nanoparticles with atom transfer radical polymerization and a grafting‐from approach. After polymerization, the magnetic nanoparticles had a graft density of 0.9 PS chains/nm2. A sacrificial initiator was used to obtain a satisfactory result for the control of the polymerization, as its addition had to generate a sufficient concentration of persistent radicals (deactivator). A variety of techniques, such as Fourier transform infrared spectroscopy, thermogravimetric analysis, gel permeation chromatography, water contact‐angle measurements, and atomic force microscopy, were used to characterize the nanoparticles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4744–4750, 2007  相似文献   

7.
Magnetic iron oxide (magnetite, Fe3O4) nanoparticles were encapsulated with polystyrene to give a stable water‐based magnetic polymer latex, using the miniemulsion polymerization technique. The resulting magnetic latexes were characterized with transmission electron microscopy (TEM), dynamic light scattering (DLS), vibrating sample magnetometer measurements (VSM), and 57Fe Mössbauer spectroscopy measurements. TEM revealed that all magnetite nanoparticles were embedded in the polymer spheres, leaving no empty polystyrene particles. The distribution of magnetite particles within the polystyrene spheres was inhomogeneous, showing an uneven polar appearance. The DLS measurements indicated a bimodal size distribution for the particles in the latexes. According to our magnetometry and Mössbauer spectroscopy data, the encapsulated magnetite particles conserve their superparamagnetic feature when they are separated in the polymer matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4802–4808, 2004  相似文献   

8.
A new, efficient method for synthesizing stable nanoparticles with poly(ethylene oxide) (PEO) functionalities on the core surface, in which the micellization and crosslinking reactions occur in one pot, has been developed. First, amphiphilic PEO‐b‐PS copolymers were synthesized by reversible addition fragmentation chain transfer (RAFT) radical polymerization of styrene using (PEO)‐based trithiocarbonate as a macro‐RAFT agent. The low molecular weight PEO‐b‐PS copolymer was dissolved in isopropyl alcohol where the block copolymer self‐assembled as core‐shell micelles, and then the core‐shell interface crosslink was performed using divinylbenzene as a crosslinking agent and 2,2′‐azobisisobutyronitrile as an initiator. The design of the amphiphilic RAFT agent is critical for the successful preparation of core‐shell interface crosslinked micellar nanoparticles, because of RAFT functional groups interconnect PEO and polystyrene blocks. The PEO functionality of the nanoparticles surface was confirmed by 1H NMR and FTIR. The size and morphology of the nanoparticles was confirmed by scanning electron microscopy, transmission electron microscopy, and dynamic laser light scattering analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

9.
Polystyrene (PS) nanocomposite particles with high titania content are prepared by Pickering emulsion polymerization. A self‐made titania hydrosol modified by an anionic monomer sodium styrene sulfonate (NaSS) is used as a stabilizer and photocatalyst. The stability of the emulsion system is greatly improved by the electrostatic interaction between negatively charged NaSS and positively charged titania nanoparticles. The nanocomposite spheres with the diameter of around 120 nm are highly charged, indicating titania‐rich surfaces of latex particles. It is also proven by the field‐emission transmission electron microscope and field‐emission scanning electron microscope images. The well‐defined core‐shell structure of the obtained PS/titania composite particles is confirmed by the formation of fragile hollow titania nanospheres after thermogravimetric analysis tests. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5728–5736, 2009  相似文献   

10.
The precipitation of Fe3O4 from an aqueous solution with ammonium hydroxide produced nanoparticles that were coated with a layer of oleic acid [or, in some cases, poly(ethylene oxide) or poly(vinylpyrrolidone)] before their dispersion into the organic phase. The encapsulation of magnetite nanoparticles in poly(2‐hydroxyethyl methacrylate) or poly(2‐hydroxyethyl methacrylate‐co‐glycidyl methacrylate) microparticles was achieved by dispersion polymerization in toluene/2‐methylpropan‐1‐ol. Magnetic poly(glycidyl methacrylate) microparticles were obtained in the presence of poly(ethylene oxide) at the magnetite/monomer interface. The particles containing up to 20 wt % iron maintained their discrete nature and did not aggregate. The effect of the reaction medium polarity, the concentrations of the monomer, initiator, and stabilizer, and the temperature on the particle size, particle size distribution, and iron and oxirane group contents was studied. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1848–1863, 2003  相似文献   

11.
In this study, we describe a new strategy for producing narrowly dispersed functional colloidal particles stabilized by a nanocomposite with hydrophilic clay faces and hydrophobic polystyrene (PS) brushes on the edges. This method involves preparation of polymer brushes on the edges of clay layers and Pickering suspension polymerization of styrene in the presence of the nanocomposites. PS brushes on the edges of clay layers were prepared by atom transfer radical polymerization. X‐ray diffraction and thermogravimetric analysis results indicated that PS chains were grafted to the edges of clay platelets. Transmission electron microscope results showed that different morphologies of clay‐PS particles could be obtained in different solvents. In water, clay‐PS particles aggregated together, in which PS chains collapsed forming nanosized hydrophobic domains and hydrophilic clay faces stayed in aqueous phase. In toluene, clay‐PS particles formed face‐to‐face structure. Narrowly dispersed PS colloidal particles stabilized by clay‐PS were prepared by suspension polymerization. Because of the negatively charged clay particles on the surface, the zeta potential of the PS colloidal particles was negative. Positively charged poly(2‐vinyl pyridine) (P2VP) chains were adsorbed to the surface of PS colloidal particles in aqueous solution at a low pH value, and gold nanoparticles were prepared in P2VP brushes. Such colloidal particles may find important applications in a variety of fields including waterborne adhesives, paints, catalysis of chemical reactions, and protein separation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1535–1543, 2009  相似文献   

12.
Luminescent poly(styrene/thiophene) (PSt/PT) core/shell nanoparticles were prepared by oxidative polymerization in the presence of PSt seed particles. PSt seed particles with uniform size distribution were prepared with an anionic surfactant by an emulsion polymerization process, and were used as a template to prepare monodispersive PT‐coated nanoparticles. A luminescent Polythiophene (PT) layer was formed on the surface of PSt nanoparticles by oxidation polymerization with iron chloride (FeCl3) and hydrogen peroxide (H2O2). The mechanism of core/shell formation was found to be the interface‐dominant polymerization induced by the electrostatic attraction between the sulfonate group of anionic surfactant and Fe3+ ions after the diffusion of thiophene monomer to the PSt nanoparticles. Field‐emission scanning electron microscopy and transmission electron microscopy (TEM) proved the core/shell structure, which provided key evidence that PT was incorporated onto the surface of PSt nanoparticles. In addition, the effect of the PT shell thickness on photoluminescent (PL) intensity was investigated by changing the shell thickness of PSt/PT nanoparticles. We observed that the PL intensity increased up to about 30 nm of PT shell thickness, and then decreased due to self‐absorption. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5968–5975, 2008  相似文献   

13.
In this research, oil‐based Fe3O4 nanoparticles were prepared by means of coprecipitation method followed by a surface modification using lauric acid. Oil‐based Fe3O4 could disperse in styrene, and polystyrene/Fe3O4 (PS/Fe3O4) composite particles were prepared via miniemulsion polymerization in the presence of potassium peroxide (KPS) as an initiator, sodium dodecyl sulphate as a surfactant, hexadecane or sorbitan monolaurate(Span 20) as a costabilizer. The effects of Fe3O4 content, homogenization energy, amount of initiator, amount of surfactant and costabilizer on the conversion, size distributions of droplets and latex particles, nucleation mechanism and morphology of composite latex particles were investigated. The results showed that different nucleation mechanisms dominated during the course of reaction when polymerization conditions changed. The most important two key factors to influence the nucleation mechanism were homogenization energy and initiator. High homogenization energy provided critically stabilized size of droplets. Otherwise, secondary nucleation, including micellar and/or homogeneous nucleation, would take place rather than droplet nucleation when a water‐soluble initiator, KPS, was used. It resulted in two populations of latex particles, pure PS particles in smaller size and PS/Fe3O4 composite particles in larger size. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1014–1024, 2008  相似文献   

14.
Atom transfer radical polymerization with activators generated by electron transfer initiating/catalytic system (AGET ATRP) of 2‐hydroxyethyl methacrylate (HEMA) was carried out in inverse miniemulsion. Water‐soluble ascorbic acid as a reducing agent and mono‐ and difunctional poly(ethylene oxide)‐based bromoisobutyrate (PEO‐Br) as a macroinitiator were used in the presence of CuBr2/tris[(2‐pyridyl)methyl]amine (TPMA) and CuCl2/TPMA complexes. The use of poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide) as a polymer surfactant resulted in the formation of stable HEMA cyclohexane inverse dispersion and PHEMA colloidal particles. All polymerizations were well‐controlled, allowing for the preparation of well‐defined PEO‐PHEMA and PHEMA‐PEO‐PHEMA block copolymers with relatively high molecular weight (DP > 200) and narrow molecular weight distribution (Mw/Mn < 1.3). These block copolymers self‐assembled to form micellar nanoparticles being 10–20 nm in diameter with uniform size distribution, and aggregation number of ~10 confirmed by atomic force microscopy and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4764–4772, 2007  相似文献   

15.
The synthesis of functionalized submicrometer magnetic latex particles is described as obtained from a preformed magnetic emulsion composed of organic ferrofluid droplets dispersed in water. Composite (polystyrene/γ‐Fe2O3) particles were prepared according to a two‐step procedure including the swelling of ferrofluid droplets with styrene and a crosslinking agent (divinyl benzene) followed by seeded emulsion polymerization with either an oil‐soluble [2,2′‐azobis(2‐isobutyronitrile)] or water‐soluble (potassium persulfate) initiator. Depending on the polymerization conditions, various particle morphologies were obtained, ranging from asymmetric structures, for which the polymer phase was separated from the inorganic magnetic phase, to regular core–shell morphologies showing a homogeneous encapsulation of the magnetic pigment by a crosslinked polymeric shell. The magnetic latexes were extensively characterized to determine their colloidal and magnetic properties. The desired core–shell structure was efficiently achieved with a given styrene/divinyl benzene ratio, potassium persulfate as the initiator, and an amphiphilic functional copolymer as the ferrofluid droplet stabilizer. Under these conditions, ferrofluid droplets were successfully turned into superparamagnetic polystyrene latex particles, about 200 nm in size, containing a large amount of iron oxide (60 wt %) and bearing carboxylic surface charges. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2642–2656, 2006  相似文献   

16.
Gold particles were nucleated on functionalized (i.e., sulfonate or imidazole groups) latex particle surfaces. Gold ions were associated with the functional groups present on the surface of the latex particles by metal‐ligand formation and were then reduced to nucleate gold particles on the particle surface. The use of imidazole groups favored the metal‐ligand formation more effectively compared with sulfonic acid groups, so gold nucleation was investigated on the surface of imidazole‐functionalized model latex particles. The desorption of gold atoms or their surface migration first occurred during the reduction process and then gold nanoparticles were nucleated. The utilization of strong reductants, such as NaBH4 and dimethylamine borane (DMAB) under mildly acidic conditions (i.e., pH 4) led to the deprotonation of imidazole‐rich polymer chains present on the surface of the model latex particles followed by deswelling of hydrophilic polymer surface layers. As a result, well‐dispersed gold nanoparticles were embedded in the hydrophilic polymer surface. On the other hand, the use of weak reductants led to the formation of localized gold aggregates on the surface of the latex particles. The removal of residual styrene monomer is very important because gold ions can be coordinated with the vinyl groups present in styrene monomer and would then be reduced by nucleophilic water addition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 912–925, 2008  相似文献   

17.
Fine magnetite nanoparticles, both electrostatically stabilized and nonstabilized, were synthesized in situ by precipitation of Fe(II) and Fe(III) salts in alkaline medium. Magnetic poly(glycidyl methacrylate) (PGMA) microspheres with core‐shell structure, where Fe3O4 is the magnetic core and PGMA is the shell, were obtained by dispersion polymerization initiated with 2,2′‐azobisisobutyronitrile (AIBN), 4,4′‐azobis(4‐cyanovaleric acid) (ACVA), or ammonium persulfate (APS) in ethanol containing poly(vinylpyrrolidone) or ethylcellulose stabilizer in the presence of iron oxide ferrofluid. The average microsphere size ranged from 100 nm to 2 μm. The effects of the nature of ferrofluid, polymerization temperature, monomer, initiator, and stabilizer concentration on the PGMA particle size and polydispersity were studied. The particles contained 2–24 wt % of iron. AIBN produced larger microspheres than APS or ACVA. Polymers encapsulating electrostatically stabilized iron oxide particles contained lower amounts of oxirane groups compared with those obtained with untreated ferrofluid. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5827–5837, 2004  相似文献   

18.
Poly(acrylic acid‐co‐sodium acrylate)/zinc oxide, P(AA‐SA)/ZnO, composite latex particles were synthesized by inverse miniemulsion polymerization. The ZnO nanoparticles were prepared by hydrothermal synthesis and undergone oleic acid (OA) surface treatment. The X‐ray diffraction pattern and FT‐IR spectra characterized the crystal structure and functional groups of OA‐ZnO nanoparticles. An appropriate formulation in preparing P(AA‐SA) latex particles, ensuring the dominant in situ particle nucleation and growth, was developed in our experiment first. Sodium hydroxide was chosen as a costabilizer, because of its ability to increase the deprotonation of acylic acid and enhance the hydrophilicity of monomer, acrylic acid besides providing osmotic pressure. The growth mechanism of P(AA‐SA)/ZnO composite particles was proposed. The OA‐ZnO nanoparticles were adsorbed on or around the surface of P(AA‐SA) latex particles by hydrophobic interaction, thus enhanced the interfacial tension over latex particles. The P(AA‐SA)/ZnO composite latex particles owned better thermal stability than pure latex particles. The pH regulation capacity was excellent for both ZnO and P(AA‐SA) particles. Combining P(AA‐SA) and ZnO nanoparticles into composite particles, the performance in pH regulation and UV shielding was discussed from our experimental results. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8081–8090, 2008  相似文献   

19.
Stable translucent aqueous suspensions of azide‐functionalized cross‐linked nanoparticles (NPs), with diameters in the 15–20 nm range, were prepared using two synthetic approaches. Copolymerization of azidomethylstyrene (VBN3), styrene, and divinylbenzene in various oil‐in‐water microemulsions led to NPs with modulable azide contents (0.53–0.78 mmol/g) and surface over volume distributions. Surface modifications of reactive NPs bearing chlorobenzyl groups, produced by microemulsion copolymerization of vinylbenzylchloride, with sodium azide led to azido‐coated NPs with high densities of peripheral groups (0.13–0.45 mmol/g). It is shown that the nature of the surfactant used for the preparation of the microemulsion has an impact on the incorporation of VBN3 in the polymer particles as well as on the surface reaction yield. The azide‐functionalized NPs were used as clickable polymeric scaffolds for the grafting of sparingly water‐soluble dansyl and fluorescein derivatives through copper(I)‐catalyzed azide‐alkyne cycloaddition in water in the presence of surfactants as solubilizing agents to produce fluorescent NPs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

20.
Micrometer magnetic hybrid particles are of great interest in biomedical field, and various morphologies have been prepared via encapsulation processes. Regarding submicron, only few processes have been investigated and the most recent one leading to highly magnetic submicron magnetic hybrid particles is based on oil in water magnetic emulsion (MES) transformation. The encapsulation of magnetic iron oxide nanoparticles forming oil in water MES was investigated using different styrene/cross‐linker divinylbenzene volume ratio in the presence of potassium persulfate initiator. The encapsulation performed in this work is basically conducted by using well‐defined oil in water MES as a seed in radical emulsion polymerization. The chemical composition, morphology, iron oxide content, magnetic properties, electrokinetic properties, particle size, and size distribution of the prepared magnetic hybrid particles were examined using various techniques. The desired perfect magnetic core and polymer shell morphology were successfully obtained, and the final magnetic hybrid particles are superparamagnetic in nature and exhibit high iron oxide content (64 wt %). Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

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