聚苯胺及其复合材料研究现状

对聚苯胺的结构、合成及其机理、质子酸掺杂 ,聚苯胺的应用 ,以及聚苯胺复合材料的研究现状进行了综合阐述 ,并详细介绍了有关煤基聚苯胺的研究情况。煤基聚苯胺和纯聚苯胺相比 ,电导率下降不大 ,而且成本降低、热稳定性增强 ;同时 ,煤基聚苯胺也为煤的非能源利用提供了新途径和新机遇 ,具有一定的推广价值。     

Preparation of conducting polysiloxane/polyaniline composites

Polysiloxane/polyaniline microcomposites were prepared, in which polyaniline particles act as filler, thus combining the mechanical properties of polysiloxane matrix with conductivity of polyaniline. Two syntheses were evaluated: (1) homogeneous dispersion of a polyaniline colloid in the reaction mixture from which the polysiloxane matrix subsequently formed, and (2) the blending of previously prepared dry polyaniline particles with a liquid oligomeric siloxane resin followed by cure (“heterogeneous method”). Both methods lead to composites with evenly distributed filler. Electrical conductivity was achieved above 40 wt % of polyaniline, which is better obtained by the “heterogeneous” method. During the composite cure, the polyaniline particles, which are softer than the matrix, act as a catalyst and cause more efficient matrix crosslinking, thus leading to somewhat raised moduli. Although particulate fillers usually deteriorate the impact toughness, in the case of the prepared composites, the impact toughness was preserved due to the softer consistence of the filler, which hinders crack propagation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42429.     

Effects of surfactants on the characteristics and biosensing properties of polyaniline

To investigate the effects of surfactants on the properties of polyaniline (PANI), a series of PANIs was synthesized in the presence of surfactants by chemical polymerization of aniline in an acidic medium, using (NH₄)₂S₂O₈ as oxidant. Three types of surfactant were used: (i) non‐ionic poly(ethylene oxide) (20) sorbitan monolaurate (Tween 20) and poly(ethylene oxide) (20) sorbitan monopalmitate (Tween 40); (ii) cationic (1‐tetradecyl)trimethylammonium bromide; and (iii) anionic sodium 1‐dodecanesulfonate and sodium 1‐pentanesulfonate. The structural, morphological and thermal properties of the various samples were characterized using Fourier transform infrared and UV‐visible spectroscopy, scanning electron microscopy and thermogravimetric analysis. Calorimetry was used to compare enthalpy changes during polymerization. The electrochemical and glucose biosensor properties of the PANIs were investigated using cyclic voltammetry and amperometric measurements. PANI‐Tween 20 and PANI‐Tween 40 were found to be good for immobilization of glucose oxidase enzymes and potential candidates for use in glucose biosensing. Copyright © 2010 Society of Chemical Industry     

Synthesis,characterization, and comparative study of conducting polyaniline/lead titanate and polyaniline–dodecylbenzenesulfonic acid/lead titanate composites

To study the effect of a surfactant on the properties of polyaniline (PANI)/metal oxide composites, PANI/lead titanate (PbTiO₃) composites were synthesized with different weight percentages (10, 20, 30, 40, and 50 wt %) of PbTiO₃ in both the absence and presence of dodecylbenzenesulfonic acid (DBSA) by the polymerization of aniline with ammonium persulfate as an initiator. The structural characteristics and stability, surface characteristics, and electric properties of PANI/PbTiO₃ and PANI–DBSA/PbTiO₃ were studied and compared. The interfacial interactions and thermal stability of these composites were characterized with X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and thermogravimetry techniques. The results indicate significant changes in the physicochemical properties of the composites with the incorporation of DBSA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Removal of chromium from waste water using polyaniline

One of the suitable methods for removing heavy metals from waste water is using surface adsorption process. In this article, the preparation of polyaniline and its composites as adsorbents are discussed and the capability of separating chromium from industrial waste water is studied. The results were compared with anthracite and cation exchangers such as purolite‐302 and amberjet. The observations indicated that the purolite and amberjet have the most chromium removal percentage. Also the role of polyaniline and its composite as adsorbents were studied. The results show that the percentage of chromium removal has increased in polyaniline/poly(vinyl alcohol) composite. Furthermore, the adsorption percentage is related to the surface morphology, type of adsorbents, and their weight ratios. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1964–1967, 2007     

Study of polyaniline polyacrylamide composites by positron annihilation technique

Polyaniline doped with nonoxidizing Bronsted acids is recognized as a conducting material, as its electrical conductivity changes with percentage of doping. In the present work, different percentages of doped polyaniline were blended with polyacrylamide and their electrical conductivities as well as the positron annihilation lifetimes were measured. Analysis of data yielded three lifetime components. It was observed that the value of the short lifetime component remained constant for doping concentration, whereas that of the intermediate component τ₂ decreased. The relative intensity pertaining to τ₂, however, increased with the increase in doped PANI concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 930–933, 2003     

聚苯胺/聚丙烯酸(酯)复合材料制备方法研究进展

聚苯胺/聚丙烯酸(酯)复合材料具有良好的可加工性、成膜性、附着力、电学性能以及防腐蚀性能。本文回顾了国内外在聚苯胺/聚丙烯酸(酯)混合复合材料和聚苯胺/聚丙烯酸(酯)聚合复合材料等方面的研究工作, 介绍了各种聚苯胺/聚丙烯酸(酯)复合材料的制备方法、性能及应用, 并比较了这些制备方法的优缺点。分析结果表明:混合复合法工艺简单、易于控制、适用范围广;聚合复合法将聚苯胺和聚丙烯酸(酯)在分子水平上结合, 使聚苯胺和聚丙烯酸(酯)的优异性能得以综合发挥;而互穿网络聚合法通过网络互穿实现了两种差别较大的分子链的强制相溶。提出在分子水平上的复合是聚苯胺/聚丙烯酸(酯)复合材料研究的主要发展方向。     

Synthesis and characterization of a composite of polyaniline and carbon black

A method is described for obtaining a composite of polyaniline and carbon black by cycling the potential of a Pt electrode in a solution containing aniline and carbon black suspension. The solution may also contain sodium dodecyl sulphate (SDS) as additive. It is shown that the rate of polymerization is enhanced by the presence of both carbon black and SDS by a factor of 5. The composite was characterized by cyclic voltammetry, scanning electron microscopy and capacity measurements.     

Enhanced adsorption of malachite green onto carbon nanotube/polyaniline composites

To enhance adsorption of organic dyes like malachite green (MG) onto polymeric absorbents, we prepared carbon nanotube (CNT) filled polyaniline (PANI) composites with large surface areas by simply using entangled CNTs as porous frameworks during PANI polymerization. Adsorption behavior of the CNT/PANI composites in MG solutions was experimentally investigated and theoretically analyzed. The CNT/PANI composites exhibit much higher equilibrium adsorption capacity of 13.95 mg g^?1 at an initial MG concentration of 16 mg L^?1, increasing by 15% than the neat PANI, which is mainly attributed to large surface areas and strong CNT‐PANI interactions of the composites. In addition, theoretical analyses indicate that the adsorption kinetics and the isothermal process of the composites can be well explained by using the Ho pseudosecond‐order model and the Langmuir model, respectively. In light of their high MG adsorption and easy operation, the CNT/PANI composites have great potential as high‐efficiency adsorbents for removal of dyes from wastewater. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The characterization of polyaniline and polypyrrole composites by pyrolysis mass spectrometry

In this work, direct insertion probe pyrolysis mass spectrometry technique was applied to investigate the thermal and structural characteristics of electrochemically prepared polyaniline (PANI), polypyrrole (PPy), and their composites/copolymers synthesized either by electrochemical polymerization of pyrrole on PANI‐coated electrode (PANI/PPy) or by coating PANI on PPy (PPy/PANI) in H₂SO₄ solutions. It has been determined that the polymer first coated on the electrode degraded to a certain extent during the polymerization of the second. The extent of degradation was greater for PPy and increased with the increase in acid concentration. On the other hand, the detection of mixed dimers confirmed copolymer formation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hybrid polyaniline/nanomagnetic particles composites: High performance materials for EMI shielding

In this work, two types of hybrid composite materials were elaborated. The first based on polyaniline (PANI) doped Camphor Sulfonic acid (CSA), Carbon‐Coated Cobalt (CCo), and FeNi nanoparticles dispersed in polyurethane. A value of 10⁴ S/m of conductivity and a 90 dB of shielding effectiveness in multilayer structure were obtained over the 8–18 GHz frequency band. The second type, based on PANI doped para‐toluene sulfonic acid (PTSA), dispersed in epoxy resin with FeNi nanoparticles. A thick material with moderate conductivity and high attenuation of electromagnetic waves was obtained. It was found that a PANI‐PTSA/FeNi/epoxy resin composite with thicknesses of 9.7 and 6.5 mm had, respectively, reflection loss values of ?22 dB at 9.52 GHz, and ?20.7 dB at 14.7 GHz. The electromagnetic properties of the elaborated structure hybrid materials can be optimized to increase the electromagnetic reflection–absorption properties. Thus, the obtained structure can be used in shielding and radar absorbing materials applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrical properties and fractal behavior of polyurethane elastomer/polyaniline composites under mechanical deformation

Present work reports on electrical properties of polyurethane elastomer/polyaniline (PU/PANI-HCl) composite films under tensile deformation. Two types of surface-modified and one type of volume-modified composite of PU and PANI-HCl were prepared. Surface modification of PU film was performed by swelling the parent film in aniline followed by its contact with the acidified oxidant solution to polymerize aniline and form PANI-HCl distributed inside surface/subsurface layer of the film. Volume-modified PU was prepared by mixing of the polymer components in a joint solution and then solution casting. Nonlinear current-voltage characteristics were observed for surface-modified samples while linear ones were typical of volume-modified samples. Deformation of the polymer composites caused partially reversible decrease of their conductivity characteristics, which could be described mathematically with a power law function of the strain with an exponent being dependable on the type of PU modification. Such behavior was interpreted in terms of deformation of a fractal percolation network formed in the system during its formation and chemical synthesis.     

原位聚合法制备聚苯胺/改性羰基铁粉复合材料

采用正硅酸乙酯(TEOS)对羰基铁粉(CIP)表面改性,通过原位聚合法制备了聚苯胺(PANI)/改性CIP复合材料。傅里叶变换红外光谱验证了SiO2和CIP表面形成了化学键。耐酸性实验表明:TEOS可在较长时间内保护CIP不被酸腐蚀,保证了制备PANI/CIP复合材料过程中CIP处于SiO2的有效保护下。所得复合材料为CIP表面包覆直径约20 nm均匀致密的PANI微粒,复合效果明显改善。复合材料电导率与CIP未改性前处于相同数量级。     

Molecular composites obtained by polyaniline synthesis in the presence of p‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10⁴ at 100 Hz) and electrical conductivity of 6 × 10^?3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ～30% (weight). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚苯胺/镍纳米复合材料的制备及其表征

以苯胺（An）、氯化镍（NiCl2×6H2O）为原料,原位聚合法合成聚苯胺/镍纳米复合微粒。采用X射线衍射仪、扫描电镜、傅里叶变换红外光谱仪、振动样品磁强计（VSM）及四探针测试仪技术表征了复合微粒的结构、形貌和电磁性能。结果表明：复合微粒在室温外加磁场下表现出铁磁性物质具有的磁滞现象,饱和磁化强度为9.44 emu/g,复合微粒在室温下的电导率为5×10-3 S/cm。     

Composites based on poly(ethylene terephthalate) fibers with polyaniline. II. The effect of the growth of the polyaniline molecules during the polymerization in the morphology of the PET substrate

PET fibers of different drawn ratios were used as substrates to produce composites with PANi. The influence of the growth of the polyaniline molecules in the structure of the fibers previously pretreated in the presence of aniline at different conditions were studied by different characterization techniques (differential scanning calorimetry, X‐ray scattering, dynamic and mechanical thermal analysis, sonic modulus, and scanning electron microscopy). The polymerization of the aniline inside the fiber substrates modified the structure of the fibers. In the case of the drawn fiber substrates the growth of the PANi molecules occurred mainly in the interfibrillar regions, which promoted reorganization of the preexisting crystals such as defect elimination (mainly in the interface of these regions with the lamellar regions) and at same time reorientation of their amorphous and crystalline regions. Also, due to this reorientation process the crystals became not only bigger and more perfect, but also they became more homogeneous. In the case of the undrawn fiber substrates, due to the lack of previous orientation, the growth of the PANi molecules would be occurring in the amorphous interlamellar regions only. Finally, the use of fibers with different drawn ratios as substrates for the composites was essential to reach such conclusions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2346–2362, 2000     

聚苯胺及其衍生物在杀菌防污领域的应用进展

抗菌剂在涂料、膜、生物智能材料等材料表面的防污领域有着极其重要的应用价值。随着环保意识的增强,长效、环境友好型的抗菌剂成为当前研究的主流。其中,聚苯胺由于其良好的生物相容性和物理化学性能,是一种极具潜力的抗菌剂。聚苯胺的抗菌机理可由自身的氧化还原活性、阳离子吸附效应及电化学活性3方面分析。概括了聚苯胺及其衍生物的结构及制备方法;进一步从杀菌防污机理出发,综述了聚苯胺及其衍生复合材料在不同防污材料中应用的研究进展,包括在接触杀菌型表面、释放杀菌型表面、抗黏附型表面3种类型的材料中的应用。此外,提出了聚苯胺在防污应用中需进一步解决的问题及发展方向。     

Hybrid nickel oxide-carbon fiber composites obtained in the presence of surfactants

The composite material nickel hydroxide (oxide)/carbon fiber has been obtained by hydroxide deposition on the surface of the activated carbon fiber (ACF) via urea hydrolysis in the presence of a surfactant. The organomineral composite NiO/CHIT/carbon fiber has been obtained by electrochemical deposition of nickel hydroxide on the ACF surface in combination with chitosan as well as by cathode deposition on a carbon fiber electrode preliminarily modified by chitosan. The surface of the obtained hybrid materials has been investigated by means of the methods of X-ray photoelectron spectroscopy (XPS), atomic force and scanning electron spectroscopy (AFM and SEM), and cyclic voltamperometry. The composition and properties of the obtained composites have been discussed.     

Synthesis and characterization of a conducting polyaniline/TiO2−SiO2 composites

Polyaniline/TiO₂?SiO₂ composites were prepared by an in situ chemical oxidation polymerization approach in the presence of hybrid TiO₂?SiO₂ fillers. The obtained polyaniline/TiO₂?SiO₂ composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FTIR), X‐ray diffraction (XRD), thermogravimetry (TG), and current?voltage (I?V) measurements. SEM picture shows a variation in morphology of polyaniline (PANI) from fiber shape to relatively regular particle shape with increasing TiO₂?SiO₂ contents in the composites. The floccule‐like structures were observed by high resolution TEM, which may help improve the efficiency of conductive network. SEM, XRD, TG, and FTIR spectra all reveal that a relatively strong interaction exist between TiO₂?SiO₂ and PANI. The I?V characteristics in such composites indicate that the charge transport is mainly governed by the space charge effects, which occurs at the interface between the conducting PANI and TiO₂?SiO₂. Meanwhile, PANI/TiO₂?SiO₂ composites exhibit significant increase in conductivity than PANI/TiO₂ or PANI/SiO₂. The reasons about high conductivity of PANI/TiO₂?SiO₂ have also been discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2288–2295, 2013     

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008