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1.
A new nanocomposite of poly(o‐methoxyaniline) (POMA) is introduced by overlayer formation of POMA on silica. The key appealing feature of the synthesis is the role of silica sulfuric acid (SSA) both as solid acid dopant and template in overlayer self‐assembly of POMA on silica surface. Hereon siloxide group (Si―O?) of silica surface is replaced with dopant anion of SSA (≡Si―O―SO3?), which leads to formation of a overlayer of POMA on the silica surface. The composite particles are spherical in the nanoscale range of 50 nm without application of any external template (no‐template synthesis). Nanocomposite was fully characterized by various instrumentation methods: Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–vis), thermogravimetric analysis (TGA), diffrential thermal analysis (DTA), elemental analysis (CHNS), energy dispersive X‐ray (EDX), X‐ray photoelectron spectroscopy (XPS) and X‐ray difraction (XRD). Based on XPS and CHNS results, it is demonstrated that the doping level of POMA is as high as 50% and for the first time the ratio of 4:2:2 is obtained for ―NH― (amine): ―HN.+― (polarons): ?HN+― (bipolarons), respectively. In fact, bipolarons may also coexist with polarons with a 1:1 ratio of them. Moreover, the synthesis benefits from the perspective of green chemistry which is preparation under solid‐state (solvent‐free) condition. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

2.
Poly(o‐methoxyaniline) (POMA) was chemically synthesized using ammonium persulfate (APS) as oxidant. Methane sulfonic acid (MSA), hydrochloric acid (HCl), and p‐toluene sulfonic acid (pTSA) were used as dopants, under the same reaction conditions. For comparison, undoped POMA was also synthesized. The polymer samples were characterized by Fourier transform infrared spectroscopy (FTIR), four‐probe conductivity measurement, scanning electron microscopy (SEM), electron spin resonance (ESR), gel permeation chromatography (GPC), and determination of specific surface area. The antioxidant activities of POMA were assessed via reaction with 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) free radical, and the anti‐microbial activities were determined as minimum bactericidal concentrations against E. coli 25422 and S. aureus 6838. When doped with relatively strong acids, high yield (above 84%) was achieved, compared to the relatively low yield (45%) when no dopant was present. The conductivity decreased in the order POMA‐pTSA > POMA‐HCl > POMA‐MSA > undoped POMA. A polaron conduction mechanism was supported by FTIR and ESR spectra. The morphology of the polymers was found to be effectively controlled by dopants. All POMA polymers showed strong free radical scavenging ability, which was highly correlated with the specific surface areas of the polymer particles. All the tested samples showed activity against S. aureus 6838, but not at the concentrations tested against E. coli 25422. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

3.
A series of poly(o‐/m‐toluidine‐coo‐/m‐aminoacetophenone) copolymers combining the features of high conductivity and processibility are synthesized and characterized by a number of techniques including 1H NMR; thermogravimetry; IR, Raman, and UV–visible spectroscopy; scanning electron microscopy; and X‐ray diffraction. The copolymers are synthesized by the emulsion and inverse emulsion methods using conventional ammonium persulfate and a new oxidant, benzoyl peroxide, respectively. The influence of the polymerization conditions such as the monomer feed ratios, solvent, and the nonsolvent is investigated. The composition of the resulting copolymers is determined by 1H NMR analysis. The conductivity of the copolymers varies with the aminoacetophenone content in the feed and the polymerization conditions. It is interesting that the conductivity of the copolymers is higher than that of the corresponding homopolymers. The results are rationalized on the basis of the effect of the ? COCH3 substituent on the polymer structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4300–4310, 2004  相似文献   

4.
Organic–inorganic composites composed of electrically conducting copolymer p‐phenylenediamine‐ co‐o‐aminophenol and carboxylic acid functionalized multi‐walled carbon nanotubes [poly(pPD‐co‐oAP)/c‐MWNTs] were prepared via in situ emulsion pathway using sodium dodecyl sulphate (SDS) as an emulsifier and potassium persulphate as an oxidant. Acid functionalized MWNTs were used as cores in the formation of tubular shells of the composites. TEM and FESEM analysis showed that a tubular layer of coated copolymer film of several nanometer thicknesses is present on the c‐MWNTs surfaces. FT‐IR spectra endorsed the formation of composites. TGA results indicated that the decomposition temperatures of composites were higher than the bare copolymer. UV‐visible absorption spectra of diluted colloidal dispersion of composites were similar to those of the bare copolymer. The composites were also confirmed by XRD and XPS. Room‐temperature conductivity increases with an increasing fraction of c‐MWNTs. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

5.
Poly(o‐aminophenethyl alcohol) and its copolymers containing the aniline unit were synthesized in aqueous hydrochloric acid medium by chemical oxidative polymerization. The chemical composition of these novel polymers was determined spectroscopically, and their viscosities were measured. These polymers exhibit good solubility in organic solvents that is attributed mainly to the polar hydroxyethyl side groups. Their structures (chain conformation and morphological structure) and properties (conductivity, electrochemical characteristics, glass transition, and degradation behavior) were characterized and then interpreted on the basis of the chemical composition along with the electronic and steric hindrance effects associated with the hydroxyethyl side group. Overall, the side group has a significant effect on the polymerization and influences the structure, chain conformation, and properties of the resultant polymer. The poly(aniline‐coo‐aminophenethyl alcohol)s containing 20–40 mol % o‐aminophenethyl alcohol units are potential conducting materials for microelectronic and electromagnetic shielding applications because they are easier to process than polyaniline but retain its beneficial properties. These polymers can also be used as a functional conducting polymer intermediate owing to the reactivity of the side group. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 983–994, 2002  相似文献   

6.
An inorganic-organic composite was prepared by poly(amidoamine) (PAMAM) dendrimer reacting with cobalt(Ⅱ)-monosubstituted polyoxometalates Na5Co^Ⅱ(H2O)PW11O39 (PW11CO) in an aqueous solution. The hybrid composite PW11Co/PAMAM was characterized by FT-IR, UV-Vis diffuse reflectance spectra (DR-UV-Vis), XPS, XRD and TG/DTA, indicating that the PWI iCo was chemically anchored to PAMAM. The morphologies of the title composite were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The catalytic activity was evaluated by oxidation of isobutyraldehyde (IBA) to isobutyric acid (IBAc) in MeCN under mild conditions (20 ℃, ambient pressure), showing that the title compound is a more effective and recoverable catalyst than corresponding PW11Co.  相似文献   

7.
A series of poly(o‐/m‐toluidine‐coo‐/m‐chloroaniline) copolymers of different compositions were synthesized by an emulsion method with ammonium persulfate as the oxidant. The conductivity of the copolymers was two to five orders of magnitude higher than that of the homopolymers poly(o‐toluidine) and poly(m‐chloroaniline). Among the copolymers, the copolymer of o‐toluidine and m‐chloroaniline exhibited a maximum conductivity of 0.14 S cm?1. The conductivity of these copolymers was also higher than that of poly(aniline‐co‐chloroaniline). The properties of the copolymers were greatly influenced by the positions of the substituents and the concentrations of the individual monomers in the feed. All the copolymers were completely soluble in polar solvents such as dimethyl sulfoxide and showed higher heat stability as the chloroaniline concentration increased. These effects could be interpreted in terms of extensive hydrogen bonding and interchain linking and, therefore, higher electron delocalization in these copolymers due to the presence of electron‐rich toluidine rings adjacent to electron‐deficient chloroaniline. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1579–1587, 2005  相似文献   

8.
Various protonated poly(o‐anisidine) (PoAN)/poly(vinyl alcohol) (PVA) composites were prepared with different types of acids: sulfuric (SA), p‐toluene sulfonic (TSA), camphor sulfonic (CSA), and p‐dodecylbenzene sulfonic (DBSA). In the visible spectrum of each composite in dimethyl sulfoxide, three absorption peaks were observed at 440, 620, and 860 nm. The peaks at 440 and 860 nm, which were enhanced with the increasing content of acid‐doped PoAN in the PVA matrix, were attributed to the radical cation and localized polaron generated in the conducting polymer. However, the peak at 620 nm was ascribed to the emeraldine base (EB) form of PoAN; that is, a portion of the acid was detached from the conducting polymer to form EB‐PoAN and free acid. The linear dependence of the logarithmic electrical conductivity on the variation of humidity, which was observed for all the composites, was caused by the salt–base transition of the conducting polymer, that is, by the movement of free acid between the active sites of the conducting polymer and the strongly bound water existing in PVA, which in turn depended directly on the environmental humidity. The response time of the composites to humidity was shortened with a decrease in the size of the dopant anions: DBSA > CSA > TSA > SA. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4343–4352, 2000  相似文献   

9.
A novel poly(aniline‐coo‐aminophenol) (PAOA)/mesoporous silica SBA‐15 nanocomposite was synthesized and investigated for adsorption of Hg (II) from aqueous solutions of wide pH range. A chemical oxidation method was employed for polymerization of aniline and o‐aminophenol on an ordered SBA‐15 template to obtain a significantly enlarged BET surface area of the adsorbent. Efficiency study revealed that the PAOA/SBA‐15 could reach a maximum Hg (II) adsorption capacity of over 400 mg/g. Kinetic study showed that the Hg (II) adsorption by the PAOA/SBA‐15 fitted a pseudo‐second‐order kinetic model, indicating that the mercury adsorption process was predominantly controlled by chemical process. The results of this study also proved that the adsorbed Hg (II) could be effectively desorbed from the PAOA/SBA‐15 in 0.1M HCl and 5% sulfocarbonide solutions. Associated adsorption mechanism was also investigated by means of Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) techniques. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

10.
The synthesis of a new A2X‐type difluoride monomer, N‐2‐pyridyl‐4′,4″‐bis‐(4‐fluorobenzenesulfonyl)‐o‐terphenyl‐3,6‐dimethyl‐4,5‐dicarboxylic imide ( 3 ), is described. The monomer 3 was incorporated into a series of copoly(aryl ether sulfone)s by polymerization of 4,4′‐isopropylidenediphenol and 4,4′‐difluorophenylsulfone. The incorporation of monomer 3 had an observable effect on both the glass‐transition temperature of poly(aryl ether sulfone)s and the tendency for macrocyclic oligomers to form during polymerization. Replacement of the pyridyl imide group via a transimidization reaction with propargyl amine proceeded quantitatively and without polymer degradation. The acetylene containing copoly(aryl ether sulfone) could be crosslinked by simple thermal treatment, resulting in an increase in the glass‐transition temperature and solvent resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 9–17, 2000  相似文献   

11.
Processable poly(m‐aminophenol) (PmAP) was synthesized using ammonium persulfate (APS) oxidant in 0.6 M sodium hydroxide solution at room temperature. Soluble silver hydroxide ammonium complex was formed by dissolving silver nitrate in excess liquor ammonia and the thermal decomposition of this complex easily produced silver nanoparticle. Then, in situ silver nanoparticle‐doped PmAP film was obtained by casting PmAP film from dimethyl sulfoxide (DMSO) with silver hydroxide ammonia complex mixture at 140°C. The nanocomposite was characterized by ultraviolet‐visible spectroscopy, Fourier transformed spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy, electron dispersion spectroscopy, thermogravimetric analysis, and X‐ray diffraction analysis. The average size of the nanoparticle was around 130–140 nm as confirmed by the TEM analysis. Synthesized PmAP silver nanocomposite showed the highest DC‐conductivity of 1.03 × 10?6 S/cm. From the above characterizations, it can be said that silver nanoparticle shows some doping effect on the conductivity of PmAP. The doping level of the silver nanoparticle inside the polymer was optimized in terms of DC‐conductivity of the silver nanoparticle‐doped PmAP film. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

12.
Poly(ethylene‐co‐vinyl acetate) (EVA) plastic films are widely used for solar coverings including photovoltaic modules and commercial greenhouse films, but are poor at controlling heat flow. In this work, silica aerogel (SA) nanogels were examined for preparing transparent heat retention EVA films that block far infrared spectra radiation to maintain heat, without compromising the optical performance of the films. SA nanogels were melt‐mixed using a mini twin‐screw extruder with EVA pellets to form SA/EVA composite, which were pressed into thin films with controlled thickness. The composite films were characterized in terms of optical properties using a variety of analytical methods including FTIR, UV–Vis spectroscopy, electron, confocal, and atomic force microscopy. Both thermicity and thermal conductivity of commercial and experimental SA/EVA films were measured. The results demonstrated that the SA/EVA films gave improved infrared retention compared to commercial thermal plastic films without compromising visible light transmission, showing the potential for this approach in next generation heat retention films. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 927–935  相似文献   

13.
Conducting poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) blends containing 10, 30, 50, 70, and 90 % wt/wt of polystyrene (PSt) were prepared by employing a two-step emulsion pathway. The bands characteristic of both polystyrene and POT/PMT are present in the IR spectra of POT–PSt and PMT–PSt blends. The UV-visible spectra of POT–PSt and PMT–PSt blends exhibit two bands around 313 and 610 nm, confirming that some amount of POT/PMT base is present in the blends. The EPR parameters such as line width and spin concentration reveal the presence of POT/PMT salt in the respective blends. The TGA, DTA, and DSC results suggest a higher thermal stability for the POT and PMT blends than that for the respective salts. The conductivity values of POT(70)–PSt(30) and POT(90)–PSt(10) blends are almost the same (1.1 × 10−2 and 1.3 × 10−2 S cm−1, respectively) and these values are very close to that of pure POT salt, suggesting that POT can be blended with up to 30% wt/wt of PSt to improve its mechanical properties without a significant drop in its conductivity. The conductivity values of PMT–PSt blends are lower than those of the corresponding POT–PSt blends by two to three orders of magnitude, indicating that POT is a better system than PMT to prepare blends by this method. The dielectric constant and tan δ values of the blends increase with the amount POT/PMT and are greater than that of polystyrene. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2291–2299, 1998  相似文献   

14.
A poly(o-methoxyaniline) (POMA)/DNA [weight fraction of DNA (W(DNA)) = 0.45] hybrid was prepared by mixing their solutions in sterilized double distilled water. The solution turned green upon aging for a longer time, and the doping of POMA by DNA was complete after about 15 d of aging. The doping was confirmed from the UV-vis spectra where the 599 nm peak of POMA(EB) disappeared and a new peak for a pi to localized polaron band-transition appeared. With increasing aging time the new peak gradually shifted from 674 nm at 3 h to 820 nm at 15 d of mixing and thereafter it remained constant. The absence of a free carrier tail in the UV-vis spectra indicated a coiled structure of POMA in the complex. Circular dichroism spectra of the hybrid solution indicated that the DNA conformation (double helical structure) remained unchanged in the hybrid. The SEM micrograph of the freeze-dried hybrid showed a needle-like morphology of the DNA dispersed in a polymer matrix and it was completely different from the fibrillar network morphology of pure DNA in the solid state. The TEM micrograph indicated a homogeneous dispersion of DNA fibrils in the POMA matrix. The melting temperature of the POMA-DNA hybrid showed an increase compared to that of pure DNA by 5 degrees C, probably caused by an electrostatic interaction between the DNA anion and the POMA radical cation generated in the doping process. WAXS investigations revealed that the DNA crystal structure remained unchanged in the hybrid whereas the POMA crystal structure might be lost. An FT-IR study suggested that interaction occurred between the phosphoric acid group of DNA and a nitrogen atom of POMA through proton transfer from the OH group of the former. A schematic model of the POMA-DNA complex randomly anchoring POMA chains with the DNA molecule was proposed. The dc conductivity of the POMA-DNA complex was found to be ca. 10(-7) S . cm(-1). Hence, this work describes a procedure for making a DNA-conducting polymer hybrid without changing the conformation and structure of DNA. [Diagram: see text]  相似文献   

15.
Three new bis(ether‐acyl chloride) monomers, 1,1‐bis[4‐(4‐chloroformylphenoxy)phenyl]cyclohexane ( 1a ), 5,5‐bis[4‐(4‐chloroformylphenoxy)phenyl]‐4,7‐methanohexahydroindan ( 1b ), and 9,9‐bis[4‐(4‐chloroformylphenoxy)phenyl]fluorene ( 1c ), were synthesized from readily available compounds. Aromatic polybenzoxazoles bearing ether and cardo groups were obtained by the low‐temperature solution polycondensation of the bis(ether‐acyl chloride)s with three bis(aminophenol)s and the subsequent thermal cyclodehydration of the resultant poly(o‐hydroxy amide)s. The intermediate poly(o‐hydroxy amide)s exhibited inherent viscosities in the range of 0.35–0.71 dL/g. All of the poly(o‐hydroxy amide)s were amorphous and soluble in many organic polar solvents, and most of them could afford flexible and tough films by solvent casting. The poly(o‐hydroxy amide)s exhibited glass‐transition temperatures (Tg's) in the range of 141–169 °C and could be thermally converted into the corresponding polybenzoxazoles approximately in the region of 240–350 °C, as indicated by the DSC thermograms. Flexible and tough films of polybenzoxazoles could be obtained by thermal cyclodehydration of the poly(o‐hydroxy amide) films. All the polybenzoxazoles were amorphous and showed an enhanced Tg but a dramatically decreased solubility as compared with their poly(o‐hydroxy amide) precursors. They exhibited Tg's of 215–272 °C by DSC and showed insignificant weight loss before 500 °C in nitrogen or air. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4014–4021, 2001  相似文献   

16.
Poly(vinylidene fluoride)(PVDF)/Na+‐MMT composites have been successfully prepared utilizing sodium montmorillonite (Na+‐MMT) via N,N‐dimethylformamide (DMF) solution mixing. The dispersion of Na+‐MMT layers in composites were investigated by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The effect of adding Na+‐MMT on crystallization behavior of PVDF was specifically studied. The β‐crystalline nucleation effect of Na+‐MMT was investigated and confirmed by differential scanning calorimetry (DSC), XRD, and Fourier transform infrared (FTIR) results. The interaction between PVDF and the surface of Na+‐MMT layers in DMF solution was confirmed by UV‐Vis absorbency. The effect of adding Na+‐MMT on rheological and electrical properties of PVDF/Na+‐MMT composites were also determined. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 903–911, 2009  相似文献   

17.
The major objective of this research was to modify the surface characteristics of poly(L ‐lactide) (PLA) by grafting a combination of hydrophilic polymers to produce a continuum of hydrophilicity. The PLA film was solvent cast, and the film surfaces were activated by ultra violet (UV) irradiation. A single monomer or combination of two monomers, selected from vinyl acetate (VAc), acrylic acid (AA), and acrylamide (AAm), were then grafted to the PLA film surface using a UV induced photopolymerization process. The film surfaces resulting from each reaction step were analyzed using ATR‐FTIR spectroscopy and contact angle goniometry. Results showed that AAm dominated the hydrophilicity of the film surface when copolymerized with VAc or AA, while the water contact angles for PLA films grafted with poly(vinyl acetate‐co‐acrylic acid) varied more gradually with feed composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6534‐6543, 2006  相似文献   

18.
Summary: Surface‐enhanced Raman scattering (SERS)‐active substrates with high enhancement were prepared by an in situ reduction method. Novel silver/poly(vinyl alcohol) (PVA) nanocomposite films were obtained, in which the silver nitrate, poly(γ‐glutamic acid) (PGA), and PVA acted as precursor, stabilizer, and polyol reducant, respectively. The UV‐visible spectra of the as‐fabricated films showed that the surface plasmon resonance (SPR) absorption band was narrow and of a stronger intensity, which indicates that the Ag nanoparticle size distribution on the substrate was highly uniform. This finding was further confirmed by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and field‐emission scanning electron microscope (FE‐SEM) measurements. It was found that a PGA‐stabilized PVA nanocomposite film revealed the presence of well‐dispersed spherical silver nanoparticles with an average diameter of 90 nm. The new substrate presents high SERS enhancement and the enhanced factor is estimated to be 106 for the detection of benzoic acid.

The Raman scattering enhancement factor for the Raman spectra of benzoic acid on the various nanocomposite films.  相似文献   


19.
Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to 1H and 13C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226  相似文献   

20.
We present a detailed study of the electric mechanism of a thin poly(o‐methoxyaniline) (POMA) field‐effect transistor. The device was prepared using Al‐Si/SiO2/(interdigitated gold lines array)/POMA structure as the gate electrode, insulating layer, source‐drain electrodes, and active layer, respectively. A model is presented for the electrical characteristics of such a device that encompasses the disordered properties of the POMA, the source‐drain electrical‐field dependence of hole mobility, and the carrier and mobility gradients in directions perpendicular to the polymer–oxide interface. The fittings of source‐drain current versus source‐drain voltage, having as parameters the gate voltage, is in good agreement with the experimental data, and the dependence of both the carrier saturation velocity and of the carrier mobility with the gate voltage are obtained. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 74–78, 2005  相似文献   

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