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1.
Hydrated sodium montmorillonite (Na‐clay) has been used as a catalyst support for the heterogeneous atom transfer radical polymerization of benzyl methacrylate in the presence of various concentrations of water, reducing agent, and CuBr2 in anisole at ambient temperature. The polymerization was promoted via reduction of CuII to CuI through the addition of sodium ascorbate (NaAsc) as a reducing agent in aqueous solution. The polymerizaton proceeded in a controlled manner and produced poly(benzyl methacylate) with moderately narrow molecular weight distribution (MWD) when performed under optimum conditions of hydration (10 wt % ≤ H2O/Na‐clay ≤ 21 wt %) and reducing agent (0.15 ≤ [NaAsc]/[I] ≤ 0.23). The polymerization was uncontrolled if hydration and NaAsc exceed above their optimum range of concentrations. Apparent rate of the polymerization (kapp) increased in the presence of decane–anisole (1/3, v/v) mixture solvent. Selective adsorption of decane at the interfaces of the hydrated clay was attributed for the rate enhancement due to increased polymer and hydrophobic interface interaction. The polymerization progressed in a controlled manner as confirmed by the first‐order time‐conversion plot, linear increase in molecular weights, and moderately narrow MWDs over conversion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

2.
Epoxy/clay nanocomposites are synthesized using clay modified with the organic modifier N,N‐dimethyl benzyl hydrogenated tallow quaternary ammonium salt (Cloisite 10A). The purpose is to investigate the influence of the clay concentration on the nanostructure, mainly on the free‐volume properties and the interfacial interactions, of the epoxy/clay nanocomposite. Nanocomposites having 1, 3, 5 and 7.5 wt. % clay concentrations are prepared using the solvent‐casting method. The dispersion of clay silicate layers and the morphologies of the fractured surfaces in the nanocomposites are studied using X‐ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The observed XRD patterns reveal an exfoliated clay structure in the nanocomposite with the lowest clay concentration (≤1 wt. %). The ortho‐positronium lifetime (τ3), a measure of the free‐volume size, as well as the fractional free volume (fv) are seen to decrease in the nanocomposites as compared to pristine epoxy. The intensity of free positron annihilation (I2), an index of the epoxy–clay interaction, decreases with the addition of clay (1 wt. %) but increases linearly at higher clay concentrations. Positron age‐momentum correlation measurements are also carried out to elucidate the positron/positronium states in pristine epoxy and in the nanocomposites. The results suggest that in the case of the nanocomposite with the studied lowest clay concentration (1 wt. %), free positrons are primarily localized in the epoxy–clay interfaces, whereas at higher clay concentrations, annihilation takes place from the intercalated clay layers.  相似文献   

3.
Metallocene catalyst based polyethylene‐co‐7‐octenyldimethyl phenyl silane (PE/Si? Ph ) and its post‐treated functional forms PE/Si? X ( X = Cl , F , OCH3 , OCH2CH3 ) were used as additives in PE/ATH composites. The impact strength of the composites was significantly increased after a small addition (0.5–3.0 wt %) of the functionalized form of the copolymer (PE/Si? X ). The thermal study of the composites gave us more information about the additive's behavior at the filler/matrix interphase and correlation to the mechanical properties was found. According to this thermal data, the original untreated form of PE/Si? Ph also seemed to interact weakly with the ATH‐filler particles, which was seen in an altered interphase at the filler/matrix boundary layer. The interaction was not strong enough to improve the impact strength of composites but an increase was observed in some other mechanical properties (tensile stress, yield strain). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5597–5608, 2005  相似文献   

4.
ABS/Clay nanocomposites were prepared using two ABS with different Acrylonitrile (AN) contents and four montmorillonite clays; a natural clay (CNa+) and three modified clays, Cloisites 10A, 20A, and 30B. The composites were prepared in a twin‐screw extruder. Results were analyzed considering the effect of clay and ABS type, on the clay dispersion, intercalation and exfoliation, as well as on the storage modulus and thermal stability of the nanocomposites. XRD and TEM confirm that when using an ABS with higher AN content (ABS2), a better dispersion and intercalation–exfoliation can be obtained. Cloisites 20A and 30B, respectively the one with greater initial intergallery spacing, but lower polarity and with smaller inter‐gallery spacing but greater polarity, produce the ABS nanocomposites with the greater intergallery spacing. Both ABS polymers have similar storage modulus and Tg and in both cases, the modulus increases with the 4 wt % clay. This increase is greater with the modified clays and slightly greater with the ABS2. Tg, from tan δ, increases very little with the 4 wt % clay, but again, this is slightly greater with ABS2. TGA and flammability tests show that the dispersed clay enhances the thermal stability and that the ABS with higher AN content produces a greater increase in fire retardancy. Tests also show that the better thermal stability and fire retardancy is obtained with the Cloisites 20A or 30B. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 190–200, 2008  相似文献   

5.
Novel water-soluble amphiphilic copolymers (poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)]) for dispersing multi-walled carbon nanotubes (MWCNTs) were used to carry out in situ methyl methacrylate (MMA) polymerization. The morphology of the poly(methyl methacrylate)/MWCNT composites and the dispersion of the MWCNTs were analyzed by transmission electron microscopy. The dispersion of multi-walled carbon nanotubes in the composites was excellent for cationic SMA (stearyl methacrylate) copolymers, even at high MWCNT loading (6.0 wt.%). The mechanical properties and electrical and thermal conductivities of the composites were also analyzed. Mechanical properties were improved by MWCNTs; the strain at break values remained stable up to 6.0 wt.% MWCNT loading. Both electrical and thermal conductivities were improved by the addition of MWCNTs.  相似文献   

6.
Polypropylene (PP)/nylon 6/clay composites were prepared by compounding of PP, which had previously been treated with two kinds of silane compounds, with a master batch composed of 90 wt % of nylon 6 and 10 wt % of octadecyl amine‐modified sodium montmorillonite (NM10). The morphology of the composites was investigated by means of SEM, TEM, XRD, and energy‐dispersive X‐ray analysis. All of the composites exhibited a phase‐separated morphology, irrespective of whether the PP was modified with the silane compounds or not. However, adhesive strength between the modified PP and NM10 was stronger than that between neat PP and NM10. Moreover, the PP grafted with 3‐(trimethoxysilyl)propyl methacrylate (PP2) reacted with the silanol groups of the clay to form PP‐clay hybrid during the compounding, which acted as a compatibilizer for the PP/nylon 6/clay composite. PP2NM composite (PP2/NM10 80/20 on weight basis) exhibited a peculiar morphology, in that the PP‐rich phase formed island domains within the nylon 6‐rich domains, which were in turn dispersed in the PP‐rich continuous matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 607–615, 2007.  相似文献   

7.
Cyanate ester (PT‐15, Lonza Corp) composites containing the inorganic–organic hybrid polyhedral oligomeric silsesquioxane (POSS) octaaminophenyl(T8)POSS [ 1 ; (C6H4NH2)8(SiO1.5)8] were synthesized. These PT‐15/POSS‐ 1 composites (99/1, 97/3, and 95/5 w/w) were characterized by X‐ray diffraction (XRD), transmission election microscopy (TEM), dynamic mechanical thermal analysis, solvent extraction, and Fourier transform infrared. The glass‐transition temperatures (Tg's) of the composite with 1 wt % 1 increased sharply versus the neat PT‐15, but 3 and 5 wt % 1 in these cyanate ester composites depressed Tg. All the PT‐15/POSS composites exhibited higher storage modulus (E′) values (temperature > Tg) than the parent resin, but these values decreased from 1 to 5 wt % POSS. The loss factor peak intensities decreased and their widths broadened upon the incorporation of POSS. XRD, TEM, and IR data were all consistent with the molecular dispersion of 1 due to the chemical bonding of the octaamino POSS‐ 1 macromer into the continuous cyanate ester network phase. The amino groups of 1 reacted with cyanate ester functions at lower temperatures than those at which cyanate ester curing by cyclotrimerization occurred. In contrast to 1 , 3‐cyanopropylheptacyclopentyl(T8)POSS [ 2 ; (C5H9)7(SiO1.5)8CH2CH2CH2CN] had low solubility in PT‐15 and did not react with the resin below or at the cure temperature. Thus, phase‐separated aggregates of 2 were found in samples containing 1–10 wt % 2 . Nevertheless, the Tg and E′ values (temperature > 285 °C) of these composites increased regularly with an increase in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3887–3898, 2005  相似文献   

8.
A series of waterborne polyurethane (WBPU)/multiwalled carbon nanotube (CNT) and WBPU/nitric acid treated multiwalled carbon nanotube (A‐CNT) composites were prepared by in situ polymerization in an aqueous medium. The optimum nitric acid treatment time was about 0.5 h. The effects of the CNT and A‐CNT contents on the dynamic mechanical thermal properties, mechanical properties, hardness, electrical conductivity, and antistatic properties of the two kinds of composites were compared. The tensile strength and modulus, the glass‐transition temperatures of the soft and hard segments (Tgs and Tgh, respectively), and ΔTg (TghTgs) of WBPU for both composites increased with increasing CNT and A‐CNT contents. However, these properties of the WBPU/A‐CNT composites were higher than those of the WBPU/CNT composites with the same CNT content. The electrical conductivities of the WBPU/CNT1.5 and WBPU/A‐CNT1.5 composites containing 1.5 wt % CNTs (8.0 × 10−4 and 1.1 × 10−3 S/cm) were nearly 8 and 9 orders of magnitude higher than that of WBPU (2.5 × 10−12 S/cm), respectively. The half‐life of the electrostatic charge (τ1/2) values of the WBPU/CNT0.1 and WBPU/A‐CNT0.1 composites containing 0.1 wt % CNTs were below 10 s, and the composites had good antistatic properties. From these results, A‐CNT was found to be a better reinforcer than CNT. These results suggest that WBPU/A‐CNT composites prepared by in situ polymerization have high potential as new materials for waterborne coatings with good physical, antistatic, and conductive properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3973–3985, 2005  相似文献   

9.
ABSTRACT

Two novel trimethacrylates, i.e., 1,1,1-tri-[4-(methacryloxyethoxy)-phenyl] ethane (TMPE) and 1,1,1-tri-[4-(2-methyl-2-methacryloxyethoxy)-phenyl]ethane (TMMPE), have been synthesized by reacting methacryloyl chloride with the corresponding hydroxyl intermediates. Both trimethacrylate monomers, having a low viscosity of 11.5 and 13.1 Pa.S, respectively, were blended with TEGDMA at three different weight ratios, i.e., 90/10, 70/30, and 50/50. The mixtures were made visible light-curable (VLC) by the addition of camphorquinone (0.5 wt%) and N,N-dimethyl-aminoethyl methacrylate (1.0 wt%). In addition to evaluation as cured neat resins, VLC formulations with 70% by wt. of silanated microfiller were also prepared and evaluated. The control in both cases was a VLC formulation of BisGMA/TEGDMA (70/30 and 50/50 wt/wt). These new, formulated resins have both improved physical properties and higher double bond conversion than the BisGMA control, as well as decreased linear polymerization shrinkage (LPS). The neat resin having 70/30 (wt/wt) ratio of TMPE/TEGDMA (T7T3, Table 2) exhibited a compressive strength (CS) of 496 (±51) MPa compared to the 70/30 (wt/wt) ratio of BisGMA/-TEGDMA control having 425(±27) MPa. A filled resin having a 90/10 (wt/wt) ratio of TMPE/TEGDMA exhibited a flexural strength (FS) of 122.6(±23) MPa, compared with a similar filled BisGMA/TEGDMA (70/30, wt/wt) resin exhibiting 112.7(±19) MPa. These and other results suggest that these new trimethacrylates have potential application in formulating dental composites with improved performance.  相似文献   

10.
A simple method has been described to remove catalyst from the copper mediated atom transfer radical polymerization (ATRP) of benzyl methacrylate and methyl methacrylate in anisole at 25 °C using hydrated natural clay (sodium montmorillonite, Na‐clay). The method consists of (1) addition of hydrated clay (CuI/clay ≈ 5 wt.‐%) either during or after the polymerization, (2) oxidation of catalyst complex by exposing the terminated reaction mixture in air, and (3) filtration to obtain catalyst free polymer solution. A strong coordination of CuBr‐ligand complex onto hydrated clay (10 wt.‐% < H2O/clay < 30 wt.‐%) upon oxidation resulted in polymers with no or insignificant residual catalyst (<1.74 ppm), as determined by UV‐vis and atomic absorption spectroscopy. The recovered clay exhibited expanded intercalary layers and absence of polymer within it.

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11.
Polyaniline/multi-walled carbon nanotube (PANI/MWNT) composites were prepared by in situ polymerization. Transmission electron microscope (TEM), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) were used to characterize the PANI/MWNT composites. Thermal stability and glass transition temperature (T g) were measured by thermogravimetry (TG) and temperature modulated differential scanning calorimetry (TMDSC), respectively. The TG and derivative thermogravimetry (DTG) curves indicated that with augment of MWNTs content, the thermal stability of PANI/MWNT composites increased continuously. While, T g increased and then decreased with the MWNTs content increasing from 0 to 20 mass%.  相似文献   

12.

A nanocomposite polymer electrolyte consisting of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) as a polymer matrix, lithium tetrafluoroborate (LiBF4) as a dopant salt, and titanium dioxide (TiO2) as an inert ceramic filler was prepared by solution casting technique. The ceramic filler, TiO2, was synthesized in situ by a sol–gel process. The ionic conductivity was investigated by alternating current impedance spectroscopy. X-ray diffraction (XRD) was used to determine the structure of the electrolyte, and its morphology was examined by scanning electron microscopy (SEM). The highest conductivity, 1.4 × 10−5 S cm−1 was obtained at 30 wt.% of LiBF4 salt addition with 6 wt.% of TiO2 filler content. Ionic conductivity was found to increase with the increase of salt concentration. The optimum value of conductivity was found at 6 wt.% of TiO2. The XRD analysis revealed that the crystalline phase of the polymer host slightly decreased with the addition of salt and filler. The SEM analysis showed that the smoother the surface of the electrolyte, the higher its conductivity.

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13.
A nanocomposite polymer electrolyte consisting of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) as a polymer matrix, lithium tetrafluoroborate (LiBF4) as a dopant salt, and titanium dioxide (TiO2) as an inert ceramic filler was prepared by solution casting technique. The ceramic filler, TiO2, was synthesized in situ by a sol?Cgel process. The ionic conductivity was investigated by alternating current impedance spectroscopy. X-ray diffraction (XRD) was used to determine the structure of the electrolyte, and its morphology was examined by scanning electron microscopy (SEM). The highest conductivity, 1.4?×?10?5 S cm?1 was obtained at 30 wt.% of LiBF4 salt addition with 6 wt.% of TiO2 filler content. Ionic conductivity was found to increase with the increase of salt concentration. The optimum value of conductivity was found at 6 wt.% of TiO2. The XRD analysis revealed that the crystalline phase of the polymer host slightly decreased with the addition of salt and filler. The SEM analysis showed that the smoother the surface of the electrolyte, the higher its conductivity.  相似文献   

14.
《Arabian Journal of Chemistry》2020,13(11):7978-7989
This work presents a study of microwave absorption properties of PAni/Fe3O4/PVA nanofiber composites with different ratio of Fe3O4 nanoparticles. The morphology of the composites nanofibers study by Field Emission Scanning Electron Microscopes (FESEM) and Transmission Electron Microscope (TEM) showed that the low content of Fe3O4 nanoparticles presence in the composites nanofibers indicates very much uniform surface, in the composites nanofiber without many bends, but some bends develop at higher content of Fe3O4 nanoparticles as indicated in the TEM image. Image-J software was used to further investigate the diameter of the composites nanofiber and found to be in the range of 152 to 195 nm. The nanofiber composites show excellent electric and magnetic properties and therefore vary with the addition of Fe3O4 nanoparticles in the composites nanofiber. In addition the PAni/Fe3O4/PVA composites nanofibers were further characterized by X-ray diffraction spectra (XRD) and Four Transformation infrared spectra (FTIR). The XRD pattern shows the presence of PAni nanotubes containing Fe3O4 nanoparticles by indicating peaks at 23.4⁰ and 35.43⁰ which was further supported by FTIR analysis. Microwave vector network analyzers (MVNA) were used to estimate the microwave absorption properties of the composites nanofibers. The absorption parameters was found to be −6.4 dB at 12.9 GHz within the range of X-band microwave absorption frequency, this reflection loss is attributed to the multiple absorption mechanisms as a result of the improved of impedance matching between dielectric and magnetic loss of the absorbent materials demonstrating that these materials can be used as protective material for electromagnetic radiation.  相似文献   

15.
Clay/poly(glycidyl methacrylate) nanocomposites (clay/PGMA) were prepared by in situ radical photopolymerization using N,N‐dimethylaminopropyltrimethoxysilane(DMA)‐modified bentonite clay acting as hydrogen donor for benzophenone in solution. This initiating system permits to photopolymerize glycidyl methacrylate between the lamellae of the DMA‐modified clay. The approach provides exfoliated nanocomposites as judged by the measurements of X‐ray diffraction. However, a low fraction of persistent intercalated clay regions was visible by transmission electron microscopy. X‐ray photoelectron spectra analyses indicate that the nanocomposites have PGMA‐rich surface. The clay/PGMA nanocomposites can be readily dispersed in ethanol. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 800–808  相似文献   

16.
N‐isopropyl acrylamide (NIPAAm) hydrogels are known as thermosensitive crosslinked polymer networks. In this work, the network parameters of their composites, i.e., NIPAAm/sodium montmorillonite (NIPAAm/Na+MMT) hydrogels synthesized by free radical solution polymerization in the presence of two different types of accelerator (tetramethyl ethylenediamine (TEMED) and ethylenediamine tetraacetic acid (EDTA)) and initiator (potassium persulphate (K2S2O8) and cerium ammonium nitrate ((NH4)2Ce(NO3)6), Ce(IV)) using five different clay content (in the range of 1.0–5.0 wt % of total monomer concentration) at 25 °C were presented and discussed. FTIR spectra, XRD patterns, SEM photographs, and network parameters of the samples indicated that the presence of COOH groups on EDTA molecules was resulted in the formation of exfoliated structures and the activity of EDTA/KPS redox pair was higher than those of TEMED/KPS and EDTA/Ce (IV) pairs. The compression moduli (G) of the hydrogels initiated with EDTA/Ce(IV) redox pair showed smooth and continual changings with increase in Na+MMT content (for swelling equilibrium at 25 °C) on the contrary of EDTA/KPS and TEMED/KPS pairs. It might be related to low initiator efficiency of cerium ammonium nitrate than KPS molecules, having higher effective crosslinking density with increasing clay content. On the other hand, the G moduli of NIPAAm/Na+MMT hydrogels (above their phase transition temperature) initiated with TEMED/KPS redox pair were higher than the others because of the more hydrophobic nature of TEMED molecules. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1256–1264, 2010  相似文献   

17.
Two methacrylate‐modified clays have been prepared and used to produce nanocomposites of polystyrene and poly(methyl methacrylate) by in situ polymerization. These nanocomposites have been characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), cone calorimetry and the evaluation of mechanical properties. When the clay contains only a single methacrylate unit, the styrene system is exfoliated but methacrylate is intercalated. When two methacrylate units are present on the cation of the clay, both systems are exfoliated. TGA data show that the thermal stability of all the nanocomposites is improved, as expected. The relationships between the fire properties and nanostructure of the nanocomposites are complicated, as shown by cone calorimetry. The conclusions that one may reach using cone calorimetry do not completely agree with those from XRD and TEM. The evaluation of mechanical properties shows an increase in Young's modulus for all nanocomposites along with a decrease in elongation; tensile strength is decreased for methacrylate nanocomposites but increased for styrenics systems. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

18.
Redox emulsion polymerization to branched vinyl polymers in the presence of 2-(tert-butylperoxy)ethyl methacrylate (BPEMA), ferrous sulfate, and sodium formaldehyde sulfoxylate (SFS) is reported in this paper. The peroxide monomer BPEMA containing alkyl peroxide was designed for high stability during preparation and storage. Nuclear magnetic resonance spectroscopy (NMR), Raman, and triple-detection size-exclusion chromatography (TD-SEC) measurements were used to reveal the polymerization procedure and provide evidence of branching structure. In the case of polymerization at St100-BPEMA1.0-FeSO4 0.5-SFS0.2, the molecular weight increased and decreased with conversion below and above 75% monomer conversion, respectively. The decreasing of molecular weight with monomer conversion came from the increased viscosity of the micelle, which makes it difficult for the formed macromolecules containing vinyl group to participate into polymerization. Finally, the molecular weight reached a value of Mn. SEC = 439,200 g/mol at 92.2% conversion. In addition, the Zimm branching factor, g', also decreased and increased with conversion below and above 60% conversion, respectively, and then the g' finally attends a value of 0.41, showing high degree of branching. Branched poly(methyl methacrylate) was also prepared through this strategy, showing a versatile approach to branched vinyl polymers.  相似文献   

19.
《Analytical letters》2012,45(14):2075-2085
This study describes the formation of composites of polyaniline (PANI)-Carbon Nanotube (CNT) using in situ chemical oxidative polymerization of the monomer aniline. The PANI-CNT composites were characterized by FTIR and UV-Visible spectroscopy and XRD method. The surface morphology of the composites was characterized by scanning electron microscopy (SEM). Pseudo-capacitive behavior of deposited PANI over the surface of CNT was investigated by means of cyclic voltammetry. The composite was mixed with activated carbon for making the electrode. The specific capacitance of the prepared electrode was tested by means of a half cell test. The PANI-CNT composite with 0.02 M aniline in initial polymerization solution had the thinnest layer and highest specific capacitance of 597.82 F/g in 1 M H2SO4.  相似文献   

20.
Poly(phenylene sulfide)/ferrosoferric oxide composites (PPS/Fe3O4) with various loading levels were prepared by melt compounding. The microstructure of composites was investigated using SEM and XRD. The rheological, electrical and magnetic properties were characterized respectively by the parallel plate rheometer, high resistance meter, and magnetometer. The results reveal that the Fe3O4 particles are well dispersed in the PPS matrix due to their nice affinity, which results in a weak strain overshoot at large amplitude oscillatory level. Both the rheological and the electrical responses of the composites show a typical percolation behavior. But the rheological percolation presents lower threshold (< 40 wt %) than that of electrical percolation (~ 50 wt %), which is attributed to the difference structure of the percolation network. The magnetic response, however, shows good linear relation with Fe3O4 loadings, indicating that the physical percolation has little influence on the magnetic properties. This is mainly due to the yielded long‐range magnetic interactions among Fe3O4 particles in the applied field, which are far stronger than those nonmagnetic physical interactions accounting for percolation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 233–243, 2008  相似文献   

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