Polymerization of aniline on polyaniline membranes

When solutions of aniline hydrochloride and ammonium peroxydisulfate were separated by a semipermeable cellulose membrane, the reactants met at the membrane and produced a polyaniline (PANI) membrane at the interface. The oxidative polymerization of aniline then proceeded in situ on the PANI-cellulose composite membrane. PANI was produced entirely at the monomer side of the membrane; about 80% conversion of aniline to PANI was observed after 24 h. The oxidation of aniline with peroxydisulfate consists in the transfer of electrons from aniline to the oxidant; it is proposed that electrons pass through the PANI membrane, which is conducting, and electroneutrality is maintained by the simultaneous transfer of protons. The reaction between aniline and peroxydisulfate thus takes place without the need for both reactant molecules to be in physical contact. The residual aniline is located only at its original side of the membrane, but the product of ammonium peroxydisulfate conversion, ammonium hydrogen sulfate, was found on both sides of the membrane. Fourier-transform infrared spectroscopy has been used to analyze PANI, the reaction residues and byproducts, and to prove that PANI is protonated with counter-ions of the sulfate type. Using this technique, we have detected only small differences in the molecular structure of PANI prepared with the membrane-separated reactants and in the polymerization when reactants were mixed; also, the molecular weights differed only marginally. The conductivity of both types of PANI was about the same. The repeated polymerization of aniline on the earlier prepared PANI-cellulose membrane yielded similar results, thus confirming the proposed concept of coupled electron- and proton-transfer through the PANI membrane.     

Chemical Oxidative Polymerization of β-Cyclodextrin/Aniline Inclusion Complex

A β-cyclodextrin (β-CD)/aniline inclusion complex has been synthesized in aqueous solution and characterized by FT-IR and ¹H-NMR spectroscopy, chemical analysis and thermogravimetric method. By elemental analysis and ¹H-NMR spectroscopy a complex with stoichiometry 1:1.95 and 1:1.8 (β-CD/aniline) respectively, is found. The complexed aniline was polymerized by chemical oxidative polymerization using ammonium peroxydisulfate in water (pH = 7) and 1M HCl aqueous solution. In both cases, after an induction period, insoluble polyanilines (PANIs) are obtained, however, in water at pH = 7, a polypseudorotaxane architecture containing a β-CD molecule to ~14 aniline units has resulted. In acidic conditions, anilinium cation is highly hydrophilic and inclusion complex has a strong tendency to dissociate to free molecules and emeraldine salt of PANI, free of host molecules is synthesized.     

Conductive elastomeric nanocomposites based on oxidation of aniline with silver nitrate via inverse emulsion polymerization

The present investigation describes a facile and rapid approach of conductive nanocomposites production and assesses the opportunity of their use as electro‐mechanical sensors. Hybrid materials containing silver and polyaniline nanoparticles reinforcing a thermoplastic elastomeric matrix were studied. The approach developed includes ultrasonically assisted in situ inverse emulsion polymerization of aniline oxidized by a weak oxidant and silver nitrate, and supported with a strong oxidant, ammonia peroxydisulfate. Aniline was doped with dodecylbenzene sulfonic acid in the presence of dissolved styrene–isoprene–styrene thermoplastic elastomer. While conventional polymerization of aniline with silver nitrate takes 2 weeks, by utilization of inverse emulsion polymerization, the reaction time reduces to 5 days. The assistance of a strong oxidant dramatically shortens the reaction time to 30 min. The technique developed results in uniform distribution of polyaniline/silver (PANI/Ag) conductive nanoparticles in the elastomeric matrix. The morphological studies of the films reveal spherically shaped 45 nm Ag particles. The presence of PANI/Ag in the styrene–isoprene–styrene elastomeric matrix enhances the electrical, thermal, and mechanical properties of the nanocomposites. The approach described provides an opportunity of the development of tunable structures and a remarkably distinctive architecture. A rapid electrical resistance response to an applied strain makes the nanocomposites developed useful as sensitive strain sensors. Copyright © 2014 John Wiley & Sons, Ltd.     

The role of acidity profile in the nanotubular growth of polyaniline

Conditions of polyaniline (PANI) nanotubes preparation were analyzed. Aniline was oxidized with ammonium peroxydisulfate in 0.4 M acetic acid. There are two subsequent oxidation steps and the products were collected after each of them. At pH > 3, neutral aniline molecules are oxidized to non-conducting aniline oligomers. These produce templates for the subsequent growth of PANI nanotubes, which takes place preferably at pH 2–3. At pH < 2, granular morphology of the conducting PANI is obtained. High final acidity of the medium should be avoided in the preparation of nanotubes, e.g., by reducing the amount of sulfuric acid which is a by-product. Reduction of the peroxydisulfate-to-aniline mole ratio was tested for this purpose in the present study. Lowering of the reaction temperature from 20°C to −4°C had a positive effect on the formation of nanotubes.     

Synthesis and properties of a newly obtained sorbent based on silica gel coated with a polyaniline film as the stationary phase for non-suppressed ion chromatography

The new sorbent for non-suppressed ion chromatography based on silica gel coated with a film of polyaniline (PANI) was obtained in a process of in situ polymerization of aniline by oxidation with ammonium peroxydisulfate. Raman analyses performed using a Thermo Scientific DXR confocal Raman Microscope equipped with the Omnic 8 software from Thermo Fisher Scientific have proved a uniform distribution of PANI on the surface of chromatographic beads and in the pores of the particle.     

BrΦnsted酸性离子液体掺杂聚苯胺的无溶剂制备及其表征

首先合成了两种带—SO3H官能团的Brφnsted酸离子液体([MIMPS][HSO4]和[PYPS][HSO4]),然后分别以这两种带—SO3H官能团的Brφnsted酸性离子液体做为掺杂剂,在无溶剂条件下通过机械化学聚合反应制备了掺杂导电态聚苯胺.由于带—SO3H官能团的Brφnsted酸性离子液体中H+可以单独以离子形式存在,因此可形成质子化导电态的翠绿亚胺盐,并以红外光谱、紫外可见-近红外、X-射线衍射、循环伏安和四探针技术等测试方法对聚苯胺进行了结构和性能表征.PANI-[MIMPS][HSO4]的结晶性、电导率和电化学活性要优于PANI-[PYPS][HSO4].     

Synthesis and characterization of red mud/polyaniline composites: Electrical properties and thermal stability

New types of conducting composites using red mud as an inorganic substrate and polyaniline as the conducting phase were prepared. Red mud/polyaniline (RM/PANI) composites were synthesized in acidic aqueous solution by the chemical oxidative polymerization of aniline using ammonium peroxydisulfate as the oxidant. The composites exhibit conductivities in the 0.42-5.2 S cm⁻¹ range, depending on the amount of polyaniline. They were characterized by infrared and UV-vis spectroscopy, scanning electron microscopy and X-ray diffraction. The IR and X-ray results show that PANI is deposited on the RM surface. The composites have a globular structure and the PANI globules synthesized on the surface of RM are smaller than those prepared under the same conditions without the substrate. Thermogravimetric analysis was used for investigation of the thermal stability of the composites. The thermal stability of the conductivity of RM/PANI composites was studied by ageing at 125 °C, the conductivity being measured in situ during this process.     

层层自组装原位聚合聚苯胺复合膜成膜机理研究

从苯胺单体出发, 通过原位聚合、现场掺杂以及基于静电力的层层自组装制备了聚苯胺复合膜. 通过苯胺活性溶液的温度及颜色变化跟踪聚合反应进程, 同时考察不同聚合反应阶段所得聚苯胺复合膜的紫外-可见吸收, 并进一步探讨聚苯胺复合膜的成膜机理. 研究表明, 成膜机制是由聚合反应初始阶段的苯胺阳离子或苯胺阳离子自由基通过静电作用快速吸附到负电性的基片表面, 形成均匀的聚合中心, 链增长生成聚苯胺; 该聚苯胺在酸性条件下经现场掺杂显电正性, 可吸附电负性的聚苯乙烯磺酸钠(PSS), 以此循环层层组装得到多层聚苯胺复合膜.     

乳液聚合中聚苯胺膜形成的动力学研究

以(NH4)2S2O8(APS)为氧化剂,十二烷基苯磺酸(DBSA)同时为乳化剂和掺杂剂,采用乳液聚合方法制备聚苯胺膜(PANIfilm),用石英晶体微天平(QCM)实时监测聚苯胺膜的形成过程,并对其动力学过程进行研究.结果表明,聚苯胺成膜反应对APS是0.5级,对苯胺是1级,聚苯胺膜增长速率随温度的升高而增加,而聚苯胺膜的最终沉积量却减小,表观活化能Ea=41.15kJ/mol,与均相溶液聚合成膜法的结果相近;随着DBSA浓度的增加,聚苯胺膜增长速率减小,而最终的沉积量增大.     

Conformational transition in polyaniline films - Spectroscopic and conductivity studies of ageing

Polyaniline films were produced in situ at room temperature from aniline hydrochloride oxidized with ammonium peroxydisulfate on glass surfaces immersed in an aqueous reaction mixture. A notable change in the character of the time dependence of resistivity at fixed temperature was observed when the temperature of ageing exceeded 85 °C. The ageing was much faster above this limit. This observation is reflected in the FTIR spectroscopic measurements on the aged protonated, as well as deprotonated, samples. The FTIR spectral variation may be explained by a conformational transition of the polymer chain at about 85 °C. The fact that a similar transition has been found with deprotonated samples indicates that this feature is an inherent property of polyaniline, and is not caused by the acid component of the PANI salt.     

模板合成H_4PMo_(11)VO_(40)/聚苯胺纳米线列阵及其聚合机理探讨

在氧化铝模板中制备了HPA/PANI纳米线列阵,SEM、TEM表明列阵中纳米线直径约为80 nm;XRD与FT-IR证明形成了有效掺杂;单根纳米线的导电率为16.2 S.cm-1;材料的TG-DTA表明PANI纳米线材料有三步失重过程,失去吸附水过程,多酸失去结晶水和PANI结构持续分解过程,多酸结构分解过程;在氧化聚合过程中H4PMo11VO40即为质子酸又为氧化剂和掺杂剂;聚合反应采用自由基机理进行,掺杂反应发生在形成醌二亚胺式自由基正离子和双苯胺式自由基正离子和醌二亚胺式自由基正离子偶联聚合成链结构时.     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis of polyaniline and application in the design of formulations of conductive paints

Polyaniline (PANI) is prepared by chemical polymerization of aniline in acidic medium using ammonium peroxydisulfate ((NH₄)₂S₂O₈) as oxidant. The polymer, with a conductivity of 25–30 S/cm, is used to formulate conducting paints. A stable paint with a conductivity of 10^?3 S/cm is obtained. Copyright © 2004 John Wiley & Sons, Ltd.     

Graphene oxide‐induced polymerization and crystallization to produce highly conductive polyaniline/graphene oxide composite

Graphene oxide (GO)–polyaniline (PANI) composite is synthesized by in situ polymerization of aniline in the presence of GO as oxidant, resulting in highly crystalline and conductive composite. Fourier transform infrared spectrum confirms aniline polymerization in the presence of GO without using conventional oxidants. Scanning electron microscopic images show the formation of PANI nanofibers attached to GO sheets. X‐ray diffraction (XRD) patterns indicate the presence of highly crystalline PANI. The sharp peaks in XRD pattern suggest GO sheets not only play an important role in the polymerization of aniline but also in inducing highly crystalline phase of PANI in the final composite. Electrical conductivity of doped GO–PANI composite is 582.73 S m^?1, compared with 20.3 S m^?1 for GO–PANI obtained by ammonium persulfate assisted polymerization. The higher conductivity appears to be the result of higher crystallinity and/or chemical grafting of PANI to GO, which creates common conjugated paths between GO and PANI. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1545–1554     

Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils

Cellulose nanofibrils (CNF) were isolated from cotton microfibrils (CM) by acid hydrolysis and coated with polyaniline (PANI) by in situ polymerization of aniline onto CNF in the presence of hydrochloride acid and ammonium peroxydisulfate to produce CNF/PANI. Nanocomposites of natural rubber (NR) reinforced with CNF and CNF/PANI were obtained by casting/evaporation method. TG analyses showed that coating CNF with PANI resulted in a material with better thermal stability since PANI acted as a protective barrier against cellulose degradation. Nanocomposites and natural rubber showed the same thermal profiles to 200 °C, partly due to the relatively lower amount of CNF/PANI added as compared to conventional composites. On the other hand, mechanical properties of natural rubber were significantly improved with nanofibrils incorporation, i.e., Young’s modulus and tensile strength were higher for NR/CNF than NR/CNF/PANI nanocomposites. The electrical conductivity of natural rubber increased five orders of magnitude for NR with the addition of 10 mass% CNF/PANI. A partial PANI dedoping might be responsible for the low electrical conductivity of the nanocomposites.     

In situ polymerization and reduction to fabricate gold nanoparticle‐incorporated polyaniline as supercapacitor electrode materials

Nanocomposites of gold nanoparticles and polyaniline are synthesized by using HAuCl₄ and ammonium peroxydisulfate as the co‐oxidant involving in situ polymerization of aniline and in situ reduction of HAuCl₄. Through these in situ methods, the synthesized Au nanoparticles of ca. 20 nm embedded tightly and dispersed uniformly in polyaniline backbone. With the Au content in composite increasing from 4.20 to 24.72 wt.%, the specific capacitance of the materials first increased from 334 to 392 F g⁻¹ and then decreased to 298 F g⁻¹. Based on the real content of PANI in composite material, the highest specific capacitance is calculated to be 485 F g⁻¹ at the Au amount of 19.15 wt.%, which remains 55.6% after 5000 cycles at the current density of 2 A g⁻¹. Finally, the asymmetric supercapacitor of AuNP/PANI||AC and the symmetric supercapacitor of AuNP/PANI||AuNP/PANI are assembled. The asymmetric supercapacitor device shows a better electrochemical performance, which delivers the maximum energy density of 7.71 Wh kg⁻¹ with power density of 125 W kg⁻¹ and maximum power density of 2500 W kg⁻¹ with the energy density of 5.35 Wh kg⁻¹.     

Polyaniline Nanotubes Prepared by One-Step Synergistic Polymerization of Aniline and Acrylic Acid

The electrochemical property of electrode materials greatly depends on their morphologies. This report introduces a novel and facile synthesis method for polyaniline (PANI) nanotubes from one-step synergistic polymerization of aniline and acrylic acid in an aqueous solution induced by the addition of ammonium persulfate (APS). The molar ratio of aniline to AA (\begin{document}$X_{\rm{ani/AA}}$\end{document}) is found to have great influence on the morphology of the produced PANI. Hollow PANI nanotubes with an average inner diameter of 80 nm and outer diameter of 180 nm can be mainly produced when \begin{document}$X_{\rm{ani/AA}}$\end{document} is not higher than 1. The electrochemical properties of the prepared PANI nanotubes have been investigated using a three-electrode system. The specific capacitance of PANI nanotubes can reach 436 F/g at a current density of 0.5 A/g in 1 mol/L H\begin{document}$_2$\end{document}SO\begin{document}$_4$\end{document} solution. Furthermore, the specific capacitance of the PANI nanotube maintains 89.2% after 500 charging/discharging cycles at a current density of 0.5 A/g, indicating a good cycling stability.     

Polyaniline-coated cellulose fibers decorated with silver nanoparticles

Cellulose fibers of 20 μm in diameter and aspect ratio of 2 or 10 were coated with protonated polyaniline (PANI) during the oxidation of aniline hydrochloride with ammonium peroxydisulfate in an aqueous medium. The presence of PANI has been proved by FTIR spectroscopy. The conductivity increased from 4.0 × 10⁻¹⁴ S cm⁻¹ to 0.41 S cm⁻¹ after coating the fibers with PANI. The percolation threshold in the mixture of original uncoated and PANI-coated fibers was reduced from 10 mass % PANI to 6 mass % PANI, as the aspect ratio changed from 2 to 10. The subsequent reaction with silver nitrate results in the decoration of PANI-coated cellulose fibers with silver nanoparticles of about 50 nm average size. The content of silver of up to 10.6 mass % was determined as a residue in thermogravimetric analysis. FTIR spectra suggest that the protonated emeraldine coating changed to the pernigraniline form during the latter process and, consequently, the conductivity of the composite was reduced to 4.1 × 10⁻⁴ S cm⁻¹, despite the presence of silver.     

Oligomer-assisted synthesis of chiral polyaniline nanofibers

We report here a novel approach to synthesize chiral PANI nanofibers in an aqueous solution. This new approach requires the following conditions: (1) Polymerization was carried out in concentrated camphor sulfonic acid solutions. (2) Aniline oligomers were used to accelerate the polymerization reaction. (3) Ammonium persulfate (oxidant) was added incrementally to the aniline solution. The high anisotropy factor of these PANI nanofibers is likely due to the "autocatalytic effect" resulting from lower oxidation potentials of aniline oligomers. Our chemical synthesis of the chiral PANI nanofibers is enantioselective and, under the optimized conditions, has an anisotropy factor (g = Deltaepsilon/epsilon) of 2.3 x 10-2.     

苯胺在聚丙烯酰胺水、乙二醇溶液中的聚合研究

以聚丙烯酰胺为反应基质,分别在聚丙烯酰胺的水、乙二醇溶液中制备了掺杂态导电聚苯胺.探索了合成可溶性导电聚苯胺的最佳条件.采用红外、紫外可见光谱、X射线粉末衍射等手段对产品进行了表征.实验结果表明,在保持聚苯胺电导率基本不变的情况下,采用在聚丙烯酰胺的乙二醇溶液中制备的聚苯胺比水溶液中制备的聚苯胺有较好的溶解率.