A promising copolymer of aniline and m-aminophenol: Chemical preparation, novel electric properties and characterization

A copolymer, poly(aniline-co-m-aminophenol), was synthesized chemically. The monomer concentration ratio strongly affects the copolymerization rate and the properties of the copolymer. A solution consisting 0.34 M aniline, 0.012 M m-aminophenol, 0.47 M ammonium peroxydisulfate and 2 M H₂SO₄ was found to be an optimum mixture for the chemical copolymerization. The visible spectra show that a high concentration ratio of m-aminophenol/aniline in the mixture inhibits the chain growth of the copolymer. The spectra of IR and ¹H NMR demonstrate that m-aminophenol units are included in the copolymer chain, which play a key role in extending usable pH region of the copolymer. The result of cyclic voltammograms in a wide potential region of −0.20-0.80 V (vs. SCE) indicates that the copolymer prepared under the optimum condition still held 52.7% of the electrochemical activity when the copolymer electrode was transferred from a solution of pH 4.0 to a solution of pH 11.0, which is much better than that of polyaniline. The X-ray diffraction spectra and images of the copolymers reveal a fact that the changes in the crystal structure and morphology of the copolymers are as a function of the monomer ratio in the mixture. The conductivity of the copolymer prepared under the optimum condition is 2.3 S cm⁻¹ and slightly depends on the pH value.     

Electrochemical copolymerization of aniline with m-aminophenol and novel electrical properties of the copolymer in the wide pH range

A copolymer, poly(aniline-co-m-aminophenol), has been synthesized using repeated potential cycling. The monomer concentration ratio, acid concentration and applied potential strongly affect the copolymerization rate and the properties of the copolymer. The optimum conditions for the copolymerization are that the scan potential range is controlled between −0.10 and 0.95 V (vs.SCE), and a solution consists of 0.34 M aniline, 0.012 M m-aminophenol and 2 M H₂SO₄. The IR spectra of the copolymers demonstrate that the m-aminophenol units are included in the copolymer chains. The cyclic voltammograms of the copolymers in 0.3 M Na₂SO₄ solution with various pH values were performed at the potential ranges from −0.20 to 0.80 V and at a scan rate of 60 mV s⁻¹. The results indicate that the copolymer still hold 41.7% of the electrochemical activity when the copolymer electrode was transferred from a solution of pH 5.0 to a solution of pH 11.0 in the potential range of −0.20 to 0.80 V. An impedance plot of the copolymer in a solution with pH 12.0 and at 0.40 V is constructed of a semicircle and a Warburg line with a slope of 1. This means that the electrode reaction of the copolymer at pH 12.0 is also under mass transfer control. The conductivity of the copolymer prepared under the optimum conditions is 1.42 S cm⁻¹, and slightly depends on the pH value. Thus, the pH dependence of the electrical properties of the copolymer is improved compared with poly(aniline-co-o-aminophenol), and is much better than that of the parent polyaniline.     

Synthesis and high electrochemical activity of poly(aniline-co-2-amino-4-hydroxybenzenesulfonic acid)

Poly(aniline-co-2-amino-4-hydroxybenzenesulfonic acid) (PAAHB) was synthesized using chemical oxidative copolymerization of aniline and 2-amino-4-hydroxybenzenesulfonic acid (AHB) in the presence of an ionic liquid at 50 °C. The conductivity of the PAAHB copolymer synthesized at the optimum conditions is 0.47 S cm⁻¹ that is lower than that of polyaniline, but is slightly affected by water. The cyclic voltammograms demonstrate that the PAAHB copolymer has excellent redox activity from highly acidic solution to pH 12.0 in a wider potential range. This is attributed to the synergistic effect of the SO₃⁻ and OH functional groups in the copolymer chain and the ionic liquid incorporated into the PAAHB film. It is evident that the pH dependence of the redox activity and conductivity of the PAAHB copolymer prepared chemically is much better than that of polyaniline, and is further improved, compared to the PAAHB copolymer prepared electrochemically. The proton NMR spectrum of the PAAHB copolymer demonstrates that the SO₃⁻ group exists in the copolymer chain instead of the SO₃H group. The ESR spectra show that the ESR signal intensity is a function of the monomer concentration ratio of AHB to aniline in the mixture. The morphology of the PAAHB copolymer is also dependent on the monomer concentration ratio in the mixture.     

Electrosynthesis of poly(aniline-co-p-aminophenol) having electrochemical properties in a wide pH range

Copolymerization of aniline and p-aminophenol in aqueous sulfuric acid solutions was electrochemically performed using cyclic voltammetry on platinum electrodes. The monomer concentration ratio can strongly affect the copolymerization rate and electrochemical property of the copolymer. The optimum conditions for the copolymerization are that the potential sweep covers the −0.20 to 0.95 V (vs. SCE) potential range, and that a solution contains 0.18 M aniline, 0.02 M p-aminophenol and 0.50 M H₂SO₄. A resulting copolymer synthesized under the optimum conditions has a good electrochemical activity in 0.50 M solutions of Na₂SO₄ with pH ≤ 10.0. IR and XPS spectra indicate that -OH groups and SO₄²⁻ ions are contained in the resulting copolymer. The SEM images reveal that the microstructure of the copolymer depends on the monomer concentration ratio during the electrolysis.     

Catalytic oxidation of xanthine by the nanostructured poly(aniline-co-2,4-diaminophenol)

Poly(aniline-co-2,4-diaminophenol) (PADAP) was synthesized in a solution containing aniline, 2,4-diaminophenol (DAP) and sulfuric acid, using potentiostatic method. The image of a PADAP film is constructed of spherical particles with an average diameter of 50 nm, which was examined by both scanning electron microscope (SEM) and atomic force microscopy (AFM). The nanostructured PADAP can catalyze xanthine oxidation under a less positive potential of 0.31 V (vs. SCE), which was proved by cyclic voltammetry and amperometric method. The PADAP electrode has a very fast response for the determination of xanthine. The response current of the PADAP electrode increases with increasing xanthine concentration and applied potential. The catalytic mechanism for the oxidation of xanthine on the nanostructured PADAP electrode is similar to that of xanthine oxidase-catalyzed reaction. Experimental evidence for the electrocatalytic mechanism of xanthine oxidation on a PADAP electrode was demonstrated via measurements of the open-circuit potential and the in situ chemical-ESR spectra of PADAP in the solutions without and with xanthine, respectively.     

Synthesis and properties of a functional copolymer from N-ethylaniline and aniline by an emulsion polymerization

A series of functional copolymers was synthesized by an emulsion polymerization of N-ethylaniline (EA) and aniline (AN) in the presence of sodium dodecylbenzene sulfonate in HCl. Several important polymer parameters including the polymerization yield, molecular weight, solubility, film formability, solvatochromism, thermochromism, and alterable electrical conductivity were systematically studied by changing the comonomer ratio, emulsifier/monomer ratio, oxidant/monomer ratio, solvent, and temperature. The resulted copolymers were characterized in detail by infrared and UV-vis spectroscopies. It is found that these copolymers exhibit narrow molecular weight distribution, good solubility, excellent film flexibility, colorful solvatochromism in various solvents, reversible thermochromism in a wide temperature range, and widely controllable conductivity from 2.03×10⁻¹⁰ to 0.161 S/cm with changing the polymerization conditions and doping states.     

Improving the electrochemical performance of polyaniline electrode for supercapacitor by chemical oxidative copolymerization with p-phenylenediamine

A series of poly(aniline-co-p-phenylenediamine) (P(ANI-co-PPDA)) copolymers were synthesized via the chemical oxidative polymerization of aniline with p-phenylenediamine (PPDA) as the comonomer. The structure and morphology of the P(ANI-co-PPDA) copolymers prepared with different feeding ratio of PPDA under different polymerizing temperature were compared with the two homopolymers polyaniline (PANI) and poly(p-phenylenediamine) (PPPDA). It is interesting to find that the electrical conductivity, specific capacitance and cycling stability of the P(ANI-co-PPDA) copolymer electrode materials were obviously improved with certain feeding ratio of PPDA, compared with those two homopolymers.     

A review on the chemical and electrochemical copolymerization of conducting monomers: recent advancements and future prospects

ABSTRACT

Synthesis of conducting polymers via copolymerization has attracted considerable attention because of their outstanding synergistic properties that can be tailored as per the requirement to produce a wide variety of functional polymers. The objective of this review is to provide insight about the unique characteristics of copolymers of conducting polymers that have been developed over the past few decades and have found potential application in solar cells, anticorrosive coatings, LEDs etc.     

Electrochemical copolymerisation of luminol with aniline: A new route for the preparation of self-doped polyanilines

Electrochemical copolymerisation of luminol and aniline from acidic aqueous medium onto gold electrodes has been investigated. Cyclic voltammetry in combination with electrochemical quartz crystal microbalance (EQCM) have been used to study both the in situ growth and redox switching process. In monomer free solution, the deposited polymers are stable and electrochemically active but distinct behaviour is shown by poly(luminol-aniline) films obtained from solutions with different monomers concentration ratio. In acidic medium, the current-voltage profiles range from a polyluminol (one pair of redox couple) to a polyaniline like redox conversion (three redox couples) as the aniline concentration increases. Unlike polyaniline, all prepared copolymers display well expressed electroactivity in sodium carbonate medium (pH 8), which also extends with the aniline content. The self-doping role assured by luminol moiety in the copolymer is also retrieved from the simultaneously recorded EQCM data.     

Chemical and electrochemical synthesis of conducting graft copolymer of acrylonitrile with aniline

A new conducting copolymer, polyacrylonitrile‐graft‐polyaniline (PAN‐g‐PANi), has been prepared by chemical and electrochemical methods from a precursor polymer. Poly[acrylonitrile‐co‐(acrylimine phenylenediamine)] (PAN‐co‐PAIPD) was synthesized chemically by reacting PAN with sodium 1,4‐phenylenediamine salt. PAN‐g‐PANi was synthesized chemically using ammonium peroxydisulfate as the oxidant and p‐toluenesulfonic acid in dimethylsulfoxide solution and adding aniline to oxidized PAN‐co‐PAIPD. Electrochemical polymerization was carried out by spin coating PAN‐co‐PAIPD on the surface of a Pt electrode, then the growth of the graft copolymer (PAN‐g‐PANi) in the presence of fresh aniline and acidic solution. The structures of the graft copolymer and PAN‐co‐PAIPD were characterized using UV‐visible, Fourier transform infrared, and ¹H and ¹³C NMR spectroscopies. The thermal properties of PAN‐g‐PANi were studied using thermogravimetric analysis and differential scanning calorimetry. Scanning electron microscopy (SEM) images showed that the morphology of PAN‐g‐PANi copolymer films was homogeneous. Electrical conductivity of the copolymer was studied using the four‐probe method, which gave a conductivity of 4.5 × 10^?3 S cm^?1 with 51.4% PANi. SEM and electrical conductivity measurements supported the formation of the graft copolymer. Copyright © 2006 Society of Chemical Industry     

The effect of electrolytic oxidation on the electrochemical properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) were electrochemically oxidized by a constant-potential electrolysis method and then investigated in detail using scanning electron microscope, transmission electron microscope, FT-IR, electrical impedance spectroscopy, and cyclic voltammetry. The FT-IR spectra showed that the amount of hydroxyl generated on the surface of MWNTs increased with increasing the electrochemical oxidation time of MWNTs. The CV results, being conducted in nitrobenzene solution, showed that the nitrobenzene reduction current increased with the increase in oxidation time of the MWNTs within the first 60 min of electrolysis. An electrical equivalent circuit model for electrical impedance spectroscopy was further established to analyze the surface capacitance and resistance of the MWNTs, and the model results showed that the capacitance of the oxidized MWNTs increased greatly while the charge transfer resistance decreased, suggesting electrochemical oxidized MWNTs modified pyrolytic carbon electrode being an effective electrochemical sensor for nitrobenzene determination.     

Fabrication and electrochemical properties of carbon nanotube film electrodes

Carbon nanotube (CNT) film electrodes were fabricated by a novel process involving the electrostatic spray deposition (ESD) of a CNT solution. Acid treated CNTs were dispersed in an aqueous solvent through sonication and then the CNT solution was electrostatically sprayed onto a metallic substrate by the ESD method. The CNT film electrodes showed well-entangled and interconnected porous structures with good adherence to the substrate. A specific capacitance of 108 F/g was achieved for the electrodes in 1 M H₂SO₄. In addition, the CNT film electrode showed good high rate capability.     

The electrocatalytic oxidative polymerizations of aniline and aniline derivatives by graphene

Graphene oxide (GO) on a glassy carbon (GC) electrode was directly reduced at −1.0 V in a phosphate buffer (pH 4.15) to form graphene/GC electrode, which was used for the electrocatalytic oxidative polymerizations of aniline, o-aminophenol, and m-aminophenol in the acidic solutions using cyclic voltammetry, amperometric and potentiometric methods. Cyclic voltammograms demonstrate that the oxidation peak of aniline on the first cycle shifts from 1.13 V on the bare GC electrode to 0.76 V on the graphene/GC electrode. In addition, both amperometric and potentiometric methods also demonstrate that graphene can effectively catalyze the electrochemical oxidative polymerization of aniline. Cyclic voltammetry confirmed that graphene can pronouncedly catalyze the electrochemical oxidative polymerizations of o-aminophenol and m-aminophenol, but graphene oxide hardly catalyzes the electrochemical oxidative polymerizations of aniline and its derivatives. The ESR spectrum of graphene is quite different from that of graphene oxide.     

Preparation and properties of polyethylene/montmorillonite nanocomposites formed via ethylene copolymerization

BACKGROUND: In situ formation of polyethylene/clay nanocomposites is one of the prevalent preparation methods that include also solution blending and melt blending with regard to process simplification, economy in cost, environment protection and marked improvement in the mechanical properties of the polymeric matrix. In the work reported here, the preparation of linear low‐density polyethylene (LLDPE) and fabrication of polymer/clay nanocomposites were combined into a facile route by immobilizing pre‐catalysts for ethylene oligomerization on montmorillonite (MMT). RESULTS: [(2‐ArN?C(Me))₂C₅H₃N]FeCl₂ (Ar = 2,4‐Me₂(C₆H₃)) was supported on MMT treated using three different methods. The MMT‐supported iron complex together with metallocene compound rac‐Et(Ind)₂ZrCl₂ catalyzed ethylene to LLDPE/MMT nanocomposites upon activation with methylaluminoxane. The oligomer that was formed between layers of MMT promoted further exfoliation of MMT layers. The LLDPE/MMT nanocomposites were highly stable upon heating. Detailed scanning electron microscopy analysis revealed that the marked improvement in impact strength of the LLDPE/MMT nanocomposites originated from the dispersed MMT layers which underwent cavitation upon impact and caused plastic deformation to absorb most of the impact energy. In general, the mechanical properties of the LLDPE/MMT nanocomposites were improved as a result of the uniform dispersion of MMT layers in the LLDPE matrix. CONCLUSION: The use of the MMT‐supported iron‐based diimine complex together with metallocene led to ethylene copolymerization between layers of MMT to form LLDPE/MMT nanocomposites. The introduction of exfoliated MMT layers greatly improved the thermal stability and mechanical properties of LLDPE. Copyright © 2009 Society of Chemical Industry     

Synthesis and physicochemical properties of graft copolymer of corn starch and acrylamide

Graft copolymerization of corn starch with acrylamide using ceric ammonium sulphate/citric acid initiation system has been studied under nitrogen atmosphere in aqueous medium. The grafting parameters are favored by increasing monomer concentration and reaction time but are affected by higher concentration of initiator and high temperature. The optimum conditions established for grafting were as follows: the concentration of initiator, 0.003 mol/L; the concentration of citric acid, 0.03 mol/L; monomer/starch, 1:1 feed ratio (w/w); reaction time, 3.0 h; and temperature, 35°C. The extent of grafting was examined by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. Both swelling power and solubility increased with the increase in temperature. Graft copolymerization increased swelling power and reduced solubility. Rapid visco‐analyzer pasting profile was studied. Graft copolymerization of corn starch results in high pasting temperature, high peak viscosity, and setback as compared with native starch. Breakdown was retarded at low percentage grafting (6.60%) but increased at high percentage grafting (60.27%). POLYM. COMPOS. 28:47–56, 2007. © 2007 Society of Plastics Engineers     

The improved electrochemical properties of novel La-Mg-Ni-based hydrogen storage composites

In the present study, a novel alloy composite has been synthesized by ball milling nonstoichiometric AB₃-type La_0.7Mg_0.3Ni_3.5 alloy with Ti_0.17Zr_0.08V_0.35Cr_0.1Ni_0.3 alloy in order to improve the cyclic stability and other electrochemical properties of La_0.7Mg_0.3Ni_3.5 alloy electrode. The phase structure, morphology and electrochemical performances of the composite have been investigated systematically. From X-ray diffraction (XRD) patterns, it can be found that the La_0.7Mg_0.3Ni_3.5 and Ti_0.17Zr_0.08V_0.35Cr_0.1Ni_0.3 alloys still retain their respective phase structures in the composite. Electrochemical studies show that the cyclic stability of the composite electrode is noticeably improved after 100 charge-discharge cycles in comparison with single La_0.7Mg_0.3Ni_3.5 alloy electrode due to enhanced anti-corrosion performance in the alkaline electrolyte. The discharge capacity retention rate C₁₀₀/C_max of composite electrode is 62.3%, which is much higher than that of the La_0.7Mg_0.3Ni_3.5 alloy electrode, although the maximum discharge capacity of the former decreases moderately. Both electrochemical impedance spectra (EIS) and linear polarization (LP) studies indicate that the electrochemical kinetics of the composite electrode is also improved. The charge-transfer resistance (R_ct), the polarization resistance (R_p) and the exchange current density (I₀) of the composite electrode are 160.2 mΩ, 129.5 mΩ and 201.6 mA/g, respectively, which are superior to those of the La_0.7Mg_0.3Ni_3.5 alloy electrode.     

Synthesis and properties of the copolymers based on aniline and 2-aminobenzyl alcohol

A kind of novel conducting copolymer with different compositions based on aniline and 2-aminobenzyl alcohol was prepared by chemical oxidative polymerization method. The copolymers were characterized by the methods of FT-IR, UV–Vis, XRD and DSC. It indicated that 2-aminobenzyl alcohol could copolymerize with aniline by this method. In addition, the solubility and conductivity of the copolymers were also studied in detail. The results showed that the copolymers had better solubility in pyridine than pure HCl doped polyaniline and the conductivities were decreased with the increase of the molar ratio of 2-aminobenzyl alcohol in copolymer.     

Conducting ferromagnetic copolymer of aniline and 3,4‐ethylenedioxythiophene containing nanocrystalline barium ferrite particles

This article reports the synthesis of conducting ferromagnetic complex of 3,4‐ethylenedioxythiophene (EDOT) and aniline (An) containing M‐type hexagonal barium ferrite (BaFe₁₂O₁₉) particles using in situ emulsion polymerization and electrochemical oxidative polymerization. Magnetic and conductivity studies reveal that the conducting ferromagnetic complex possesses high‐saturation magnetization (M_s) value of 29.2 emu/g and conductivity of the order of 0.256 S/cm determined through vibrating sample magnetometer and four‐probe method. Microwave measurement has shown the reflection loss (R_L) of ?12.1 dB in Ku‐band that can be used as a microwave absorbing material. The polymer complex was further characterized by techniques like X‐ray diffraction, Fourier transform infrared, UV–visible, cyclic voltammetry, and thermal analysis with thermogravimetric analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effect of Ti3AlC2 precursor on the electrochemical properties of the resulting MXene Ti3C2 for Li-ion batteries

The presented work compared the etching behavior between combustion synthesized Ti₃AlC₂ (SHS-Ti₃AlC₂) and pressureless synthesized Ti₃AlC₂ (PLS-Ti₃AlC₂). Because the former had a more compact structure, it was harder to be etched than PLS-Ti₃AlC₂ under the same conditions. When served as anode material for Li-ion batteries, SHS-Ti₃C₂ showed much lower capacity than PLS-Ti₃C₂ at 1?C (52.7 and 87.4?mAh?g^?1, respectively) due to the smaller d-spacing. Furthermore, Potentiostatic Intermittent Titration Technique (PITT) was used to determine the Li-ion chemical diffusion coefficient (${\mathrm{D}}_{{\mathrm{Li}}^{+}}$) of Ti₃C₂ in the range of 10^?10 ??10^?9 cm² s^?1, indicating that Ti₃C₂ could exhibit an excellent diffusion mobility for Li-ion.