硅钨酸掺杂聚苯胺催化剂催化合成丁酮乙二醇缩酮

报道了以H4SiW12O40(硅钨酸)／PAn(聚苯胺)为催化剂,通过丁酮和乙二醇反应合成了丁酮乙二醇缩酮,探讨了H4SiW12O40／PAn对缩酮反应的催化活性,较系统地研究了酮醇物质的量比,催化剂用量,反应时间诸因素对产品收率的影响。实验表明：在n酮：n醇=1：1．5,催化剂用量为反应物料总质量的0．60％,环己烷为带水剂,反应时间2．0h的优化条件下,丁酮乙二醇缩酮的收率可达70．1％。     

Preparation and enhanced capacitance of core–shell polypyrrole/polyaniline composite electrode for supercapacitors

Polypyrrole (PPy) nanotubes were synthesized by using the complex of methyl orange (MO)/FeCl₃ as a template. Then the core–shell polypyrrole/polyaniline (PPy/PANI) composite was prepared by in situ chemical oxidation polymerization of aniline on the surface of PPy nanotubes. The morphology and molecular structure were characterized by transmission electron microscopy (TEM), infrared spectroscopy (IR) and X-ray diffraction (XRD). TEM images confirmed that the composite was core–shell nanotubes. The electrochemical properties of the PPy/PANI composite electrode were investigated by cyclic voltammetry (CV), galvanostatic charge–discharge and electrochemical impedance spectroscopy (EIS). The electrochemical experiments showed that the specific capacitance of the PPy/PANI composite was 416 F g⁻¹ in 1 M H₂SO₄ electrolyte and 291 F g⁻¹ in 1 M KCl electrolyte. Furthermore, the composite electrode exhibited a good rate capability and maintained 91% of initial capacity at a current density of 15 mA cm⁻² in 1 M H₂SO₄ electrolyte.     

Control of polyaniline conductivity and contact angles by partial protonation

Many studies require a specific value of conductivity when investigating conducting polymers. The conductivity of polyaniline can efficiently be controlled by partial protonation of the polyaniline base. Although this is a simple task in principle, practical guidelines are missing. In the present study, the changes in the conductivity of polyaniline base after immersion in aqueous solutions of various acids are reported. Polyaniline base has been reprotonated in aqueous solutions of picric, camphorsulfonic and phosphoric acids. The conductivity of partially reprotonated polyaniline varied between 10⁻⁹ and 10⁰ S cm⁻¹. The relation between the pH of a phosphoric acid solution, which was in equilibrium with polyaniline, and the conductivity σ is pH = 0.77 − 0.64 log(σ [S cm⁻¹]). The wettability, i.e. water contact angles, can similarly be set by partial protonation to between 78° for polyaniline base and 44° for polyaniline reprotonated in 1 mol L⁻¹ phosphoric acid. In solutions of picric acid, the transition from the non‐conducting to the conducting state occurs over a narrow range of acid concentrations, and the tuning of conductivity is consequently difficult. Phosphoric acid is well suited for the control of conductivity of polyaniline because of the moderate dependence of the conductivity on the acid concentration or pH. Copyright © 2007 Society of Chemical Industry     

纳米聚苯胺在均相反应介质中的合成与导电性能研究

在丙酮、丁二酮水溶液中采用化学氧化法合成纳米聚苯胺，并研究有机溶剂的含量对纳米聚苯胺导电性能的影响。通过傅里叶变换红外光谱仪、紫外分光光度计、扫描电镜对其分子结构及微观形貌进行表征。两探针法测试结果表明，在丙酮水溶液中合成的纳米聚苯胺电导率从0．0295 S／cm（纯水介质）提高到0．5640 S／cm；表面电阻从201．28Ω／cm（纯水介质）降至14．89Ω／cm（丙酮体积分数为25％）；在丁二酮水溶液中合成的纳米聚苯胺电导率提高至0．4590 S／cm；表面电阻降低至15．57Ω／cm（丁二酮体积分数为50％）。     

Dispersion polymerization of aniline using hydroxypropylcellulose as stabilizer: role of rate of polymerization

Hydroxypropylcellulose (HPC) has been used as a steric stabilizer for preparing polyaniline dispersions using the route of oxidative dispersion polymerization of aniline. Using strongly acidic conditions (1 mol l^?1 HCl), low temperature of about 2 °C and a concentration of aniline as low as 0.5%, ammonium peroxodisulfate at 1.25% and hydroxypropylcellulose concentrations at 0.5–1 g d l^?1, unstable dispersions were obtained not only in water but also in aqueous alcohols (ethanol and methanol) up to at least 70 vol% alcohol. In contrast, dispersions that remained stable for at least 72 h were obtained when the alcohol concentration of the medium was as high as about 80 vol%. Kinetic studies of the polymerization systems suggested that success in the latter case was due to a lowering of the rate of polymerization. Transmission electron microscopy studies showed that dispersion particles prepared in 80 vol% alcohol media are spherical in shape and their diameter decreases with increasing stabilizer concentration. However, a change of morphology from spherical to aggregated needle‐shaped was observed when the rate was increased by increasing the aniline concentration from 0.5% to 0.75% g d l^?1 in the above recipe. The aggregated particles were found to be broken down to spherical nanoparticles when the as‐prepared dispersions were sonicated for about 30 min. The sonicated dispersion on drying showed the presence of fractal clusters of polyaniline particles in the dried film. The fractal dimension was determined to be 1.77 which agreed well with the theoretical value determined by computer simulation based on a diffusion limited cluster–cluster aggregation model in three dimensions. © 2001 Society of Chemical Industry     

Removal of N‐methylpyrrolidone hydrogen‐bonded to polyaniline free‐standing films by protonation–deprotonation cycles or thermal heating

Free‐standing films of polyaniline (PANI), in an emeraldine base state, prepared by evaporation of polymer solutions in N‐methylpyrrolidone (NMP) retain solvent even under dynamic vacuum drying as indicated by transmission Fourier transform infrared (FTIR) spectroscopy, where a band at 1670 cm^?1 is clearly observed. Upon protonation–deprotonation cycles in aqueous media the weight of the dry base film decreases indicating gradual loss of NMP. Transmission FTIR spectra shows also the washing out of NMP with a clear decrease in intensity of the hydrogen‐bonded >C?O stretching band (1670 cm^?1) of NMP. During this process the bands between 3500 and 3200 cm^?1, assigned to >N? H stretching in the PANI backbone, change intensity suggesting that intermolecular hydrogen‐bonded >N? H, with carbonyl oxygen of NMP, is replaced by free >N? H. This is clear evidence of specific interaction of NMP with the emeraldine base. A similar loss of NMP is observed during heating but evidence of polymer degradation is also present. A mechanism is proposed to account for the loss of hydrogen‐bonding ability upon protonation which requires delocalization of the radical cations in the protonated films. © 2001 Society of Chemical Industry     

The mechanism of the oxidative polymerization of aniline and the formation of supramolecular polyaniline structures

Polyaniline is one of the most important conducting and responsive polymers. A molecular mechanism for the oxidation of aniline is proposed. This mechanism explains the specific features of aniline oligomerization and polymerization in various acidity ranges. The formation of polyaniline precipitates, colloids and thin films is reviewed and discussed on the basis of the chemistry of aniline oxidation. The generation of nanostructures, i.e. granules, nanotubes, nanowires and microspheres, is also considered. Oligomers containing phenazine constitutional units play an important role in self‐assembly to form templates. Polyaniline chains then grow from these templates and produce the various individual morphologies. Copyright © 2008 Society of Chemical Industry     

Polyaniline-multiwalled carbon nanotube composites: Characterization by WAXS and TGA

Polyaniline/carboxylated multi-walled carbon nanotube (PAni/c-MWNT) nanocomposites have been synthesized by micellar aided emulsion polymerization with various c-MWNTs compositions, viz., 0.5, 1, 5, and 10 wt %. The microcrystalline parameters such as the nanocrystal size (〈N〉), lattice strain (g), interplanar distance (d_hkl), width of the crystallite size distribution, surface weighted crystal size (D_s), and volume of the ordered regions were calculated from the X-ray data by using two mathematical models, namely the Exponential distribution and Reinhold distribution methods. The effects of heat ageing on the microcrystalline parameters of the PAni/c-MWNT nanocomposites were also studied and the results are correlated. The thermal stability and electrical resistivity of the PAni/c-MWNT nanocomposites were examined with thermogravimetric analysis (TGA) and a conventional two-probe method. The TGA data indicate that the thermal stability of the nanocomposites improved after the incorporation of c-MWNTs. The influence of temperature on the resistivity of the nanocomposites was also measured. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of polyaniline films using Fenton reagent

The chemical oxidation of aniline to form polyaniline (PANI) films and powder samples was made using Fenton reagent as an oxidizing agent in aqueous sulfuric acid medium. The PANI films were monitored by using the quartz crystal microbalance and the electronic absorption techniques. The optimum concentration was determined and the results were justified by measuring the UV–vis absorption spectra for the in situ PANI films. The conductivity for the PANI films and powder samples, prepared in different conditions, was measured. Also, the IR spectra, X‐ray and the thermogravimetric analysis for the PANI powder formed in the bulk were measured and compared with the polymer prepared using ammonium peroxydisulfate. A preliminary investigation to the dielectric properties of the polymer powder was measured and discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚苯胺晶性问题的探讨

用广角X射线衍射(WAXD),SEM,DSC和TGA方法研究了聚苯胺的晶性问题,结果表明,不同条件下所得聚苯胺其本征型的结晶行为差别较大。当聚合溶液的酸浓度在0.001～7N范围内时,随着酸浓度增加,其本征态聚合物的结晶性降低。所得产物的掺杂态较本征态更容易结晶,结晶度随掺杂剂浓度的升高而增加。适当的热处理可提高聚苯胺的结晶能力。