聚苯胺/介孔碳纳米线复合电极材料的制备和性能

以介孔碳纳米线为基体, 通过电化学方法制备了新型聚苯胺/介孔碳纳米线(PANI/MCFs)复合材料, 采用SEM和TEM等手段对样品的结构和形貌进行了表征. 结果表明, 聚苯胺均匀附在介孔碳纳米线表面, 并填充到纳米线介孔孔道中. 将复合材料组装成三电极体系超级电容器, 用循环伏安、 恒流充放电和交流阻抗等方法对材料的电化学性能进行了测试. 结果显示, 在1 mol/L H₂SO₄溶液中, 复合材料的比电容达到391 F/g, 其循环稳定性也得到显著提高.     

Preparation and characterization of polyaniline-containing Na-AlMCM-41 as composite material with semiconductor behavior

Composite material formed from a mesoporous aluminosilicate, Na-AlMCM-41, with conducting polyaniline (PANI) has been synthesized by an in situ polymerization technique. Studies of aniline adsorption over mesoporous Na-AlMCM-41 synthesized in our laboratory allowed us to find the modes in which aniline interacts with the active sites of Na-AlMCM-41. In order to obtain the best reaction conditions to polymerize aniline onto Na-AlMCM-41, aniline was first polymerized to produce pure PANI. Hence, the oxidative in situ polymerization was carried out by two procedures, differing in the polymerization time and in static or stirring conditions. Studies of infrared spectroscopy and UV-vis spectroscopy indicated that higher polymerization time and static conditions allowed us to obtain mainly polyaniline in emeraldine form on the host. The N(2) isotherm of the polyaniline/Na-AlMCM-41 composite (PANI/MCM) indicated that the shape was similar to that of MCM, but the shift to saturation transition to lower partial pressure shows that the channels are occupied by PANI and they are now narrowed. The thermal properties of PANI, Na-AlMCM-41, and composite were investigated by TGA analyses and we found that the polymer shows higher thermal stability when it is forming the composite. Scanning electron microscopy indicated that PANI is not on the outer surface of the host. Conductivity studies show that PANI/Na-AlMCM-41 exhibits semiconductor behavior at room temperature and its conductivity was 7.0 x 10(-5) S/cm, smaller than that of pure polyaniline. PANI/Na-AlMCM-41 conductivity shows an increase as temperature increases. Magnetic measurements at room temperature confirmed that the composite has paramagnetic behavior; at lower temperatures the composite became diamagnetic.     

Designing Polyaniline (PANI) and Polyvinyl Alcohol (PVA) Based Electrically Conductive Nanocomposites: Preparation,Characterization and Blood Compatible Study

Novel electrically conducting and biocompatible composite hydrogel materials comprising of poly (aniline) (PANI) nanoparticles dispersed in a poly (vinyl alcohol) (PVA) – g–poly (acrylic acid) (PAA) matrix were prepared by in situ polymerization of aniline. The prepared ionic hydrogels were evaluated for their water uptake capacity in distilled water. While structural insights into the synthesized polymer was sought by Fourier Transform Infrared (FTIR) spectroscopy and X–Ray Diffraction (XRD) techniques, morphology and dimension of PANI particles embedded into the colored optically semi–transparent polymer films were evaluated by Scanning Electron Microscopy (SEM) analysis and Transmittance Electron Microscopy (TEM) while thermal behavior of composite hydrogel was investigated by Differential Scanning Calorimetry (DSC). Electrical conductivity of composite hydrogels containing different PANI percentage was determined by LCR. Considering the potential of electrically conductive nanocomposites materials in biomedical applications the in vitro blood compatibility of nanocomposites was investigated by employing several in vitro tests.     

Electrochemical Polymerization of Aniline in Polyamide and Polyvinyl Alcohol Matrices

The electrochemical polymerization of aniline was studied in polymer matrices (polyamid-12 and polyvinyl alcohol) on an electrode in the potential cycling mode from –0.2 to +0.8 V vs. SCE. The indices of this process such as the potentials and currents of the polyaniline redox peaks, polymerization rate, and properties of the conducting composite formed depend on the nature of the matrix polymer and are a function of the extent of interaction of this matrix polymer with aniline and polyaniline.     

Composite materials based on polyaniline and multiwalled carbon nanotubes: Morphology and electrochemical behavior

Composites based on polyaniline are prepared via the chemical oxidative polymerization of aniline in the presence of multiwalled carbon nanotubes modified by the sorption of the co-oxidants IrC ₆ ^2? and 2,2′-azino-bis(3-ethyl-benzthiazolin-6-sulfonate). The approach used here, in combination with corresponding conditions of polymerization, ensures the synthesis of composite materials with a high morphological homogeneity of the polymer phase. The study of the electrochemical properties of composites (the reversibility of redox transitions and the stability of capacity parameters) indicates that that they are strongly influenced by the morphological features of the polymer coating. The composite prepared with the use of nanotubes modified by 2,2′-azino-bis(3-ethyl-benzthiazolin-6-sulfonate) possesses better electrochemical characteristics. This effect is associated with a closer to perfect morphology of the polymer coating, a coaxial polyaniline shell highly uniform in thickness along the entire length of nanotubes.     

Structure and characteristics of composite materials based on polyaniline and Nylon-6

A comparative systematic study addresses the specific features of polymerization of aniline adsorbed on the Nylon matrices in the solutions containing monomer and in the monomer-free solutions. The characteristics of the formed composite materials are investigated. In the presence of aniline in the solution, a uniform and conducting composite material is obtained and its electrical conductivity reversibly depends on pH of the medium and is several orders of magnitude higher than the electrical conductivity of the composite material prepared by the polymerization of aniline in the Nylon matrix in the monomer-free solution.     

The morphology of composite polymer particles produced by multistage soapless seeded emulsion polymerization

 Composite polymer particles which contain poly(methyl methacrylate) (PMMA) and polystyrene (PS) components (PMMA/PS composite particle) were synthesized by the method of multistage soapless seeded emulsion polymerization. In this study, the process of multistage soapless seeded emulsion polymerization included two-stage polymerization, three-stage polymerization or four-stage polymerization. The morphologies of the PMMA/PS composite particles were studied. The kinetic factor was the main force to control the morphology of the linear PMMA–PS composite particles which were synthesized by the method of two-stage reaction. Both the kinetic factor and the thermodynamic factor decide the morphology of the linear composite particles which were synthesized by the method of either three-stage or four-stage reaction. However, the thermodynamic factor cannot influence the morphology of the PMMA/PS composite particles with a cross-linked structure which were synthesized by the method of three-stage reaction. The cross-linked composite polymer particles had the morphology of a multilayer structure, which showed that the polymer layers accumulated in their order of production. Received: 9 January 2001 Accepted: 14 June 2001     

超疏水聚苯胺/聚四氟乙烯复合膜的制备及油-水乳液分离性能

以苯胺为原料, 采用原位聚合法在聚四氟乙烯(PTFE)基体上合成聚苯胺/聚四氟乙烯(PANI/PTFE)复合膜. 利用光学显微镜、 扫描电子显微镜(SEM)、 傅里叶变换红外光谱(FTIR)、 紫外-可见吸收光谱(UV-Vis)和静态水接触角测试对PANI/PTFE复合膜的形貌、 结构和浸润性进行分析, 并对其油包水乳液分离性能、 通量和循环使用性能进行了测试. 研究结果表明, PANI/PTFE复合膜仅在重力条件就能有效分离油包水乳液; 而且重复数十次过滤后, PANI/PTFE复合膜仍具有良好的抗污能力和分离性能.     

Production of micron-sized, monodispersed, multihollow polystyrene/poly(3,5-xylidine) composite particles by chemical oxidative seeded polymerization

 Micron-sized, monodispersed polystyrene/poly(3,5-xylidine) composite polymer particles were produced by chemical oxidative seeded polymerization of 3,5-xylidine with 1.37-μm-sized, monodispersed polystyrene seed particles. The chemical oxidative seeded polymerization was conducted in an aqueous medium at 25 °C in the presence of poly(vinyl alcohol) as a stabilizer using ammonium persulfate as an oxidant. The composite particles had a multihollow structure. Received: 30 June 1999/Accepted in revised form: 21 October 1999     

Poly(tetrafluoroethylene) composite membranes coated with urchin-like polyaniline hiberarchy: Preparation and properties

Spiny polyaniline (PANI) spheres (urchin-like) were coated on a poly(tetrafluoroethylene) (PTFE) membrane via a counter-diffuse interfacial oxidation polymerization of aniline in an aqueous medium. The produced composite membrane has both unexpected superhydrophilicity and conductivity. The microstructure and morphology of the composite membrane were characterized by FTIR, UV-vis, XRD, TGA, and SEM. Effects of reagent concentrations and polymerization time on the membrane morphology and properties were studied systematically. A possible formation mechanism of the urchin-like polyaniline nanospheres on PTFE surface has been briefly discussed. The co-effect of both spherical micelles formed by Nafion and nanofibrous micelles formed by aniline/p-toluenesulfonic acid was considered to be a reason to produce the urchin-like PANI nanospheres. The PTFE/Nafion/PANI composite membrane showed a convertible hydrophilic/hydrophobic feature via adjusting acidity/alkalinity of an aqueous medium and also was able to adsorb heavy metal-ions from the medium.     

Synthesis of novel fluorescent molecule and its polymeric form with aniline as fluorescent and supercapacitor electrode materials

In this study, a fluorescent material, 2‐naphthyl‐4‐amino benzoate, is synthesized by the esterification of 4‐aminobenzoic acid with 2‐naphthol. This molecule is used in the bulk polymerization of aniline, which results in the formation of poly(aniline‐2‐naphthyl‐4‐aminobenzoate). For comparison, polyaniline and also poly(aniline‐4‐aminobenzoic acid) salts are prepared via bulk polymerization. Formation and properties of these polymeric materials are evaluated by Fourier‐transform infrared (FT‐IR), ¹³C nuclear magnetic resonance, matrix‐assisted laser desorption ionization, UV‐Vis, Fluorescence, X‐ray diffraction (XRD), Field emission‐scanning electron microscopy (FE‐SEM), Differential scanning calorimetry (DSC), thermogravimetric analysis, electrical resistance and electrochemical techniques. P(ANI‐2NA4ABA) is obtained in nanofiber morphology in 106 wt% yield with respect to the amount of aniline used with comparable conductivity of conventional polyaniline salts. This polymer salt is stable up to 220°C and indicates melting at 146°C on heating and crystal formation at 128°C on cooling. This polymer shows higher wavelength fluorescence compared to the conventional polyaniline salts. This polymer is used as an electrode material without binder, which shows a specific capacitance of 360 F g^?1 at 0.25 A g^?1.     

聚苯胺-木质素磺酸复合物的合成及其染料吸附性能——介绍一个综合性研究型实验

以苯胺为单体,木质素磺酸为分散剂,采用化学氧化聚合法合成成本低廉、吸附性能优异的聚苯胺-木质素磺酸(PAL)复合物。要求学生掌握复合物的合成操作步骤、复合物的表征及其染料吸附性能测试的方法。通过对比实验结果,为研究型实验教学提供思路。该实验利于加深学生对高分子学科知识的理解与运用,培养他们的综合实验能力。     

Amperometric glucose biosensor based on platinum nanoparticle encapsulated with a clay

Electrically conductive hollow nanospheres with an average diameter between 100 and 200 nm were prepared via a one-step polymerization of aniline in the presence of lignosulfonate (LS) by using ammonium persulfate (APS) as the oxidant. The LS concentration and molar ratio between APS and aniline, the temperature and time for polymerization were adjusted to optimize morphology, structure and electrochemical properties. Uniform hollow nanospheres are best obtained at a concentration of 18 wt% of LS, at a polymerization temperature at 25 °C, at an APS/aniline molar ratio of 1:1, and at a polymerization time of 1 to 12 h. This kind of preparation of nanospheres represents a simple and general route to polymer hollow nanospheres of controllable size, high stability, and optimizable electroconductivity.     

氧化还原低温引发MMA/BA超浓乳液薄层共聚合的研究

以甲基丙烯酸甲酯-丙烯酸丁酯(MMA-BA)作为混合单体、以乳化剂十二烷基硫酸钠(SDS)和共乳化剂十六烷醇(CA)作为复合乳化剂体系、聚乙烯醇(PVA)为液膜增强剂,制备了稳定的超浓乳液.以过氧化二苯甲酰(BPO)和N,N′-二甲基苯胺(DMA)为氧化还原引发体系,用一种新的超浓乳液薄层技术,在较低温度下引发共聚合.探讨了液膜增强剂种类和聚合环境对聚合稳定性影响;研究了薄层厚度,薄层面积,聚合温度和加热方式对体系(包括单体和水)挥发性和转化率的影响.比较了薄层和试管聚合的速率.用透射电子显微镜观察了水浴与烘箱加热方式下聚合物乳胶粒的形态,得到了在水浴中反应后的聚合物粒子平均粒径和分散度都减小的结果.     

Polymerization of some sulfur-containing oxetanes

Polymerization under the influence of boron trifluoride of 2-oxa-6-thia[3,3]spiroheptane gives two products: a linear polyether containing oxetane groups and a crosslinked polyether polysulfide. When the polymerization was carried out at ?3°C., up to 60% of soluble polysulfide is obtained. This does not prove that the thietane group polymerizes more rapidly than the oxetane group but rather that oxetane polymerization is inhibited by the presence of thietane groups. Polymerization under the influence of boron trifluoride etherate of 3,3-bis(mercaptomethyl)oxetane leads to a polyether containing free thiol groups. The degree of polymerization of the polymer, however, is low. In order to obtain higher degrees of polymerization several compounds with masked thiol groups were polymerized. 2-Oxa-6,7-dithia-6-thio[3,4]spirooctane and 2-oxa-6,8-dithia-7,7-dimethyl[3,5]-spirononane gave crosslinked products. The diacetate of 3,3-bis(mercaptomethyl)oxetane gave a linear polyether containing thiolacetate groups. Hydrolysis of this polymer leads to poly-3,3-bis(mercaptomethyl)oxetane with a softening temperature of 125–135°C.     

Pseudo Capacitive Studies of Polyaniline-Carbon Nanotube Composites as Electrode Material for Supercapacitor

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 H₂SO_4.     

Electrochemical Template Synthesis of an Polyaniline Composite with Polymeric Perfluorinated Sulfo Cationite

Combining a tracer technique with electrochemical measurements offers a unique opportunity to study the mechanism of anodic synthesis of a composite based on an electron-conducting polymer (polyaniline) and a polymeric perfluorinated sulfo cationite (Nafion, MF-4SK). The composite formation involves two steps. First, the monomer (aniline) is intercalated into the solid-cationite matrix probably with the formation of a template phase, after which postintercalation polymerization of the template occurs.     

Synthesis of Au nanoparticle-conductive polyaniline composite using H2O2 as oxidising as well as reducing agent

We report a new method of synthesis of an Au nanoparticle-conductive polyaniline composite by using H2O2 both for reduction of HAuCl4 and polymerization of aniline in the same aqueous medium: the electrical conductivity of the composite has been measured to be two orders of magnitude higher than the polymer itself.     

苯胺在十二烷基苯磺酸/水体系中的乳液聚合过程研究

利用光学显微镜和扫描电镜,对以水为介质、十二烷基苯磺酸(DBSA)为乳化剂的苯胺乳液聚合过程进行监测,发现苯胺在水体系中与DBSA反应形成DBSA-苯胺盐的棒状聚集结构,讨论了DBSA、苯胺、氧化剂的配比及浓度对聚合过程中棒状聚集结构的长度和数量及生成聚苯胺的电导率的影响,提出苯胺在DBSA/水体系中的乳液聚合反应是在胶束表面进行的,而棒状聚集结构中的DBSA-苯胺盐单体经水相扩散到乳胶粒子中,形成颗粒状的聚苯胺.     

Immobilization of phthalocyanines in conducting polymers. Polyaniline-copper tetrasulfophthalocyanine

Interaction between the anilinium cation and copper tetrasulfophthalocyanine anion (CuTSPc) was studied in an aqueous sulfuric acid solution using electronic absorption spectra. It was shown that up to 0.15 M aniline could be introduced into the solution at the dye concentration of 10⁻³ M, after which a solid deposit of a complex (salt) between the anilinium cation and copper tetrasulfophthalocyanine anion started precipitating rapidly. The effect of the dye on the kinetics of aniline polymerization on conducting glasses and on the properties of the polymer obtained was studied. It was found that phthalocyanine accelerates electropolymerization of aniline and is immobilized within the polymer matrix. It was shown that the self-catalytic synthesis mechanism characteristic of polyaniline is also preserved in the case of the composite of polyaniline-copper tetrasulfophthalocyanine.