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1.
Microencapsulated phase change materials (MePCMs) using melamine–formaldehyde resin/SiO2 as shell were investigated in this paper. Organically modified SiO2 particles were employed to stabilize Pickering emulsion, and in situ polymerization of melamine and formaldehyde was carried out to form hybrid shell. The performances of resultant MePCMs with hybrid shell were investigated comparatively with the MePCMs with polymer shell. SiO2 particles raise the microencapsulation efficiency by improving the stability of emulsion and providing a precipitation site for melamine–formaldehyde resin. Also, the mechanical strength, thermal reliability, and anti‐osmosis performance of MePCMs were improved significantly by SiO2 particles in the shell. Our study shows that Pickering emulsion is a simple and robust template for MePCMs with polymer‐inorganic hybrid shell. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

2.
Hollow molecular imprinted polymer microspheres were prepared by distillation precipitation polymerization with (S)‐(+)‐ibuprofen (S‐IBF) as template molecule and acrylamide (AM) as functional monomer. Using the silicon dioxide (SiO2, 180 nm) modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) as the template microspheres, the molecular imprinted shells were coated on successfully (SiO2@MIPs). The thermosensitive SiO2@MIPs‐PNIPAM core‐shell microspheres were subsequently prepared by grafting the PNIPAM chains (Mn=1.21×104 g/mol, polydispersity index=1.30), which were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization, on the surface of SiO2@MIPs microspheres via the thiol‐ene click chemistry. The grafting density of PNIPAM brushes on the SiO2@MIPs microspheres was about 0.18 chains/nm2. After HF etching, the hollow imprinted microspheres were finally obtained. For thermosensitivity analysis, the phase transition temperatures of multifunctional nanoparticles were measured by DSL at 25°C and 45°C respectively, and the sizes of the microspheres changed by about 35 nm. The modified microspheres presented excellent controlled release property to S‐IBF, moreover about half amount of the adsorptions passed into acetonitrile‐water solution through the specific holes of imprinted shell at 25°C under vibration.  相似文献   

3.
A novel microphase‐inversion method was proposed for the preparation of TiO2–SiO2/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006  相似文献   

4.
We aim to develop novel photoresponsive surface molecularly imprinted polymer (SIMP) microspheres, an SiO2‐SIMP, for the photocontrolled extraction of uric acid from biological samples. The SiO2‐SMIP was prepared on silica microspheres by surface polymerization and characterized by using scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, thermogravimetric analysis, nitrogen adsorption–desorption analysis, and UV‐visible spectroscopy. The SiO2‐SMIP microspheres showed a photocontrolled uptake and release of uric acid in NaH2PO4 buffer upon alternate irradiation at 365 and 440 nm. The SiO2‐SMIP microspheres were able to photocontrollably extract uric acid from complicated biological samples for concentration analysis with no significant interference encountered and it exhibited very good recognition ability and fast binding kinetics toward uric acid.  相似文献   

5.
We report a facile method that combined sol–gel reaction, reversible addition–fragmentation chain transfer (RAFT)/macromolecular design via interchange of the xanthates process and thiol‐ene click reaction to prepare monodisperse silica core‐poly(N‐vinylimidazole) (PVim) shell microspheres of 200 nm in average diameters. First, silica with C = C double bonds was prepared by the sol–gel reaction of 3‐(trimethoxysilyl)propyl methacrylates (MPS) with tetraethoxysilane in ethanol; SiO2@PVim were subsequently prepared by grafting PVim chain (Mn = 9800 g/mol, polydispersity index = 1.22) to MPS‐SiO2 via the thiol‐ene click chemisty. The obtained SiO2@PVim microspheres show higher catalytic activity toward the hydrolysis of p‐nitrophenyl acetate compared with the PVim homopolymers. The as‐prepared composites have been characterized by scanning electron microscopy, transmission electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectrometry analysis. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

6.
Optically active polyurethane/titania/silica (LPU/TiO2/SiO2) multilayered core–shell composite microspheres were prepared by the combination of titania deposition on the surface of silica spheres and subsequent polymer grafting. LPU/TiO2/SiO2 was characterized by FT-IR, UV–vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), SEM and TEM, and the infrared emissivity value (8–14 μm) was investigated in addition. The results indicated that titania and polyurethane had been successfully coated onto the surfaces of silica microspheres. LPU/TiO2/SiO2 exhibited clearly multilayered core–shell construction. The infrared emissivity values reduced along with the increase of covering layers thus proved that the interfacial interactions had direct influence on the infrared emissivity. Besides, LPU/TiO2/SiO2 multilayered microspheres based on the optically active polyurethane took advantages of the orderly secondary structure and strengthened interfacial synergistic actions. Consequently, it possessed the lowest infrared emissivity value.  相似文献   

7.
《Electroanalysis》2017,29(5):1443-1450
In this study, inorganic/organic composites containing poly (N‐isopropylacrylamide) coated core‐shell SiO2 microspheres were prepared via surface‐initiated atom transfer radical polymerization (ATRP). The thermal responsive polymer, N‐isopropylacrylamide was treated with methanol, water and CuBr/CuBr2/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) at room temperature to form PNIPAM@SiO2 microspheres. The as‐prepared PNIPAM@SiO2 microspheres were characterized by FT‐IR, TGA, XPS, SEM, TEM analyses. Hemoglobin (Hb) was immobilized onto the surfaces of PNIPAM@SiO2 microspheres via hydrophobic and π‐π stacking interactions. The as‐prepared Hb/PNIPAM@SiO2 electrode exhibits well‐defined redox peak at a formal potential of −0.38 V, validating the direct electrochemistry of Hb. The Hb immobilized composite film retained its bioelectroactivity without any significant loss of catalytic activity. The modified electrode detects H2O2 over a wide linear concentration range (0.1 μM to 333 μM) with a detection limit of 0.07 μM. This modified electrode also successfully detects H2O2 from food and disinfectant samples with appreciable recovery values, validating its practicality. We believe that PNIPAM@SiO2 composite has great potential to be used in the detection of H2O2 and development of other enzyme based biosensors.  相似文献   

8.
The preparation of Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe3O4@polyaniline composites is reported. Fe3O4 nanoclusters were first synthesized through the solvothermal method and then the SiO2 shell was coated on the Fe3O4 surface via a sol–gel process. To prepare Fe3O4@SiO2@polyaniline composites, polyvinylpyrrolidone was first grafted on to the surface of Fe3O4@SiO2 composites and subsequently polymerization of aniline was carried out via an ultrasound‐assisted in situ surface polymerization method. Selective etching of the middle SiO2 layer was then accomplished to obtain the yolk–shell Fe3O4@polyaniline composites. The approach uses polyaniline (PANI) conductive polymer as a template for the synthesis of Ni@Pd core–shell nanoparticles. The catalytic activity of the synthesized yolk–shell Fe3O4@PANI/Ni@Pd composite was investigated in the reduction of o‐nitroaniline to benzenediamine by NaBH4, which exhibited conversion of 99% in 3 min with a very low content of the catalyst. Transmission electron microscopy, X‐ray photoelectron spectroscopy, TGA, X‐ray diffraction, UV–visible, scanning electron microscopy, X‐ray energy dispersion spectroscopy and FT‐IR were employed to characterize the synthesized nanocatalyst. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

9.
Double‐shelled zirconia/titania (ZrO2/TiO2) hollow microspheres were prepared by the selective removal of the polymer components via the calcination of the corresponding tetra‐layer poly(N,N′‐methylenebisacryl amide‐co‐methacrylic acid) (P(MBA‐co‐MAA))/Zr(OH)4/poly(ethyleneglycol dimethacrylate‐co‐methacrylic acid) (P(EGDMA‐co‐MAA))/TiO2 hybrid microspheres. These tetra‐layer microspheres were synthesized by the combination of the distillation copolymerization of N,N(‐methylenebisacryl amide‐co‐methacrylic acid (MBA) or ethyleneglycol dimethacrylate (EGDMA) crosslinker and methacrylic acid (MAA) for the preparation of polymer core and third‐layer as well as the controlled sol‐gel hydrolysis of inorganic precursors for the construction of zirconium hydroxide (Zr(OH)4) and titania (TiO2) layers. The thicknesses of zirconia and titania shell‐layers were conveniently controlled via varying the feed of zirconium n‐butoxide (Zr(OBu)4) and titanium tetrabutoxide (TBOT) during the sol‐gel hydrolysis, while the sizes of polymer layers were tuned through a multi‐stage distillation precipitation copolymerization. The structure and morphology of the resultant microspheres were characterized by transmission electron microscopy (TEM), X‐ray diffractometer (XRD), X‐ray photoelectronic spectroscopy (XPS), and thermogrametric analysis (TGA).  相似文献   

10.
Many ionic liquids (ILs) have good solubilities of CO2 but the high viscosity of ILs makes them cumbersome and kinetically limits gas uptake. Encapsulation of ILs is an effective approach to overcoming these limitations. In capsules with a core of IL, the chemical composition of the shell impacts performance. Here, we report the preparation of capsules with a core of the IL [Bmim][PF6] and polymer composite shell, then evaluate how the identity of the polymer impacts CO2 uptake. IL-in-oil Pickering emulsions stabilized by nanosheets are used, with capsules formed by interfacial polymerization between different diamines and diisocyanates (e.g., shells are polyurea and nanosheets). The capsules contain 60–80 wt% IL and the composition was verified using Fourier transform infrared spectroscopy. Optical microscopy, scanning electron microscopy, and particle sizing data showed spherical, discrete capsules with 50–125 μm in diameter. All capsules are stable up to 250°C. Brunauer–Emmett–Teller analysis of CO2 gas uptake data showed that different polymer compositions led to different CO2 uptake properties, with capacity ranging from 0.065 to 0.025 moles of CO2/kg sorbent at 760 torr and 20°C. This work demonstrates that the polymer identity of the shell impacts gas uptake properties and supports that shell composition can tailor performance.  相似文献   

11.
Jiapeng Li  Qihui He  Renfu Xu  Baixing Hu 《中国化学》2015,33(11):1259-1268
In this paper silica nanoparticles with covalently grafted polymer chains were incorporated into bisphenol A dicyanate ester (BADCy) to prepare composites which resulted in improvements in the mechanical and thermal properties. Fourier‐transform infrared (FT‐IR) spectroscopy transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) were employed to examine the surface functionalization of silica nanoparticles. The effects of functionalized SiO2 (F‐SiO2) on the curing reactivity mechanical and thermal properties of BADCy resin were investigated systematically. The curing reaction of the system was facilitated with the addition of F‐SiO2. Meanwhile compared with the neat resin the incorporation of appropriate content of modified F‐SiO2 can enhance the mechanical properties including impact flexural strengths and fracture toughness KIC of BADCy resin. In addition the thermal stability of BADCy/F‐SiO2 nanocomposites is also superior to that of pure BADCy resin.  相似文献   

12.
Amino‐functionalized nanosilica (SiO2‐NH2) was prepared through cocondensation method using aminopropyltriethoxysilane as comonomer to hydrolyze and cocondense with tetraethylorthosilicate. The synergistic effect of combination of ammonium polyphosphate and pentaerythritol with SiO2‐NH2 on the thermal and flame‐retardant properties of intumescent flame‐retardant (IFR) polypropylene (PP) has been investigated by thermogravimetric analysis (TGA), scanning electron microscopy, Raman spectra, X‐ray diffraction (XRD), limiting oxygen index (LOI), and UL 94 tests. When 1.0 wt.% SiO2‐NH2 was added, the LOI value of the PP/IFR composite with 25 wt.% of IFR increased from 26.6% to 31.7%, while the UL 94 rating raised from not classified to V‐0. The TGA data demonstrated that the SiO2‐NH2 nanoparticles increased the charred residue of the PP/IFR composites. The morphological structures and the orderliness of the charred residue proved that SiO2‐NH2 promoted the formation of compact intumescent charred layer, which effectively protected the underlying polymer from burning. The XRD patterns of the charred residue indicated that nanosilica reacted with APP to form SiP2O7 crystal structure during combustion, which was beneficial to the formation of compact charred layers. In comparison with the inorganic SiO2‐cal nanoparticles, the amino‐functionalized nanosilica revealed much more efficient synergistic flame‐retardant effect due to the difference of surface properties.  相似文献   

13.
A magnetic solid‐phase extraction adsorbent that consisted of citrus peel‐derived nanoporous carbon and silica‐coated Fe3O4 microspheres (C/SiO2@Fe3O4) was successfully fabricated by co‐precipitation. As a modifier for magnetic microspheres, citrus peel‐derived nanoporous carbon was not only economical and renewable for its raw material, but exerted enormous nanosized pore structure, which could directly influence the type of adsorbed analytes. The C/SiO2@Fe3O4 also possessed the advantages of Fe3O4 microspheres like superparamagnetism, which could be easily separated magnetically after adsorption. Integrating the superior of biomass‐derived nanoporous carbon and Fe3O4 microspheres, the as‐prepared C/SiO2@Fe3O4 showed high extraction efficiency for target analytes. The obtained material was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and the Brunauer–Emmett–Teller method, which demonstrated that C/SiO2@Fe3O4 was successfully synthesized. Under the optimal conditions, the adsorbent was selected for the selective adsorption of seven insecticides before gas chromatography with mass spectrometry detection, and good linearity was obtained in the concentration range of 2–200 μg/kg with the correlation coefficient ranging from 0.9952 to 0.9997. The limits of detection were in the range of 0.03–0.39 μg/kg. The proposed method has been successfully applied to the enrichment and detection of seven insecticides in real vegetable samples.  相似文献   

14.
The determination of morphine concentration in the blood and urine is necessary for patients and recruitment purposes. Herein, a magnetic molecularly imprinted polymer for selective and efficient extraction of morphine from biological samples was synthesized by using a core–shell method. Fe3O4 nanoparticles were coated with SiO2‐NH2. The molecularly imprinted polymer was coated on the Fe3O4/SiO2‐NH2 surface by the copolymerization of methacrylic acid and ethylene glycol dimethacrylate in the presence of morphine as the template molecule. The morphological and magnetic properties of the polymer were investigated. Field‐emission scanning electron microscopy indicated that the prepared magnetic polymer is almost uniform. The saturation magnetization values of Fe3O4 nanoparticles, Fe3O4/SiO2‐NH2, and the magnetic polymer were 48.41, 31.69, and 13.02 emu/g, respectively, indicating that all the particles are superparamagnetic. Kinetics of the adsorption of morphine on magnetic polymer were well described by second‐order kinetic and adsorption processes and well fitted by the Langmuir adsorption isotherm, in which the maximum adsorption capacity was calculated as 28.40 mg/g. The recoveries from plasma and urine samples were in the range of 84.9–105.5 and 94.9–102.8%, respectively. By using the magnetic molecularly imprinted polymer, morphine can selectively, reliably, and in low concentration be determined in biological samples with high‐performance liquid chromatography and UV detection.  相似文献   

15.
SiO2/TiO2 composite microspheres with microporous SiO2 core/mesoporous TiO2 shell structures were prepared by hydrolysis of titanium tetrabutylorthotitanate (TTBT) in the presence of microporous silica microspheres using hydroxypropyl cellulose (HPC) as a surface esterification agent and porous template, and then dried and calcined at different temperatures. The as-prepared products were characterized with differential thermal analysis and thermogravimetric (DTA/TG), scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption. The results showed that composite particles were about 1.8 μm in diameter, and had a spherical morphology and a narrow size distribution. Uniform mesoporous titania coatings on the surfaces of microporous silica microspheres could be obtained by adjusting the HPC concentration to an optimal concentration of about 3.2 mmol L−1. The anatase and rutile phase in the SiO2/TiO2 composite microspheres began to form at 700 and 900 °C, respectively. At 700 °C, the specific surface area and pore volume of the SiO2/TiO2 composite microspheres were 552 and 0.652 mL g−1, respectively. However, at 900 °C, the specific surface area and pore volume significantly decreased due to the phase transformation from anatase to rutile.  相似文献   

16.
The improvement of mechanical properties and toughness of nanoparticles for epoxy composites was mostly dependent on the disperse state of nanoparticles in epoxy matrices. When the content of nanoparticles was higher than a threshold value, it was easy to aggregate and then affect the improvement effect. Pickering emulsion was prepared using SiO2 nanoparticles as emulsifier and functional monomer as oil phase. The influence of Pickering emulsion on the curing process was investigated. The effect of Pickering emulsion on the mechanical properties, toughness, and glass transition temperature (Tg) was studied. Impact and tensile fracture surface were observed by scanning electron microscopy (SEM). Results from differential scanning calorimeter (DSC), tensile, impact, and fracture toughness tests are provided. The results indicated that the introduction of Pickering emulsion can eliminate the residual stress and accelerate curing reaction. Epoxy composites were capable of increasing tensile strength by up to 29.9%, impact strength of three‐fold, fracture toughness of 35%, and Tg of 20.7°C in comparison with the reference sample. SEM images showed that SiO2 nanoparticles exhibit a good dispersion in epoxy matrix. The increases in mechanical properties, toughness, and Tg of epoxy composites were attributed to the “Second Phase Toughness” mechanism.  相似文献   

17.
A novel silica‐based stationary phase with branched octadecyl groups was prepared by the sequential employment of the Michael addition reaction and photoinduced thiol–yne click chemistry with 3‐aminopropyl‐functionalized silica microspheres as the initial material. The resulting stationary phase denoted as SiO2‐N(C18)4 was characterized by elemental analysis, FTIR spectroscopy and Raman spectroscopy, demonstrating the existence of branched octadecyl groups in silica microspheres. The separations of benzene homologous compounds, acid compounds and amine analogues were conducted, demonstrating mixed‐mode separation mechanism on SiO2‐N(C18)4. Baseline separation of basic drugs mixture was acquired with the mobile phase of acetonitrile/H2O (5%, v/v). SiO2‐N(C18)4 was further applied to separate Corydalis yanhusuo Wang water extracts, and more baseline separation peaks were obtained for SiO2‐N(C18)4 than those on Atlantis dC18 column. It can be expected that this new silica‐based stationary phase will exhibit great potential in the analysis of basic compounds.  相似文献   

18.
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  相似文献   

19.
A strategy has been developed for the synthesis, characterization and catalysis of magnetic Fe3O4/P(GMA‐EGDMA)‐NH2/HPG‐COOH‐Pd core‐shell structure supported catalyst. The P(GMA‐EGDMA) polymer layer was coated on the surface of hollow magnetic Fe3O4 microspheres through the effect of KH570. The core‐shell magnetic Fe3O4/P(GMA‐EGDMA) modified by ‐NH2 could be grafted with HPG. Then, the hyperbranched glycidyl (HPG) with terminal ‐OH were modified by ‐COOH and adsorbed Pd nanoparticles. The hyperbranched polymer layer not only protected the Fe3O4 magnetic core from acid–base substrate corrosion, but also provided a number of functional groups as binding sites for Pd nanoparticles. The prepared catalyst was characterized by UV–vis, TEM, SEM, FTIR, TGA, ICP‐OES, BET, XRD, DLS and VSM. The catalytic tests showed that the magnetic Fe3O4/P(GMA‐EGDMA)‐NH2/HPG‐COOH‐Pd catalyst had excellent catalytic performance and retained 86% catalytic efficiency after 8 consecutive cycles.  相似文献   

20.
In present work, silica pillared montmorillonite material (C‐SiO2‐OMT) was prepared via the sol–gel method, and the influence of the powder on thermal stability and flammability performance of polypropylene (PP) composites was investigated. Characterization of C‐SiO2‐OMT, elucidated with X‐ray diffraction, transmission electron microscopy, and N2 adsorption–desorption, suggested that the powder had a mesoporous lamellar structure with high specific surface area and mesoporous volume. The formation of porous structure of C‐SiO2‐OMT was more conducive than organically modified montmorillonite (OMT) to slowing the volatilization of pyrolytic products generated during thermal degradation process, which led to PP/C‐SiO2‐OMT microcomposite show better thermal stability than PP/OMT nanocomposite at high temperature range. Flammability properties of these polymer materials evaluated by microscale combustion calorimetry, and cone calorimetry showed a contrary tendency, but C‐SiO2‐OMT holds high promise to reduce the smoke yield. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

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