Synthesis and characterization of conducting homopolymers and copolymers of o‐anisidine and o‐toluidine in inorganic and organic supporting electrolytes

The influence of inorganic and organic supporting electrolytes on the electrochemical, optical, and conducting properties of poly(o‐anisidine), poly(o‐toluidine), and poly(o‐anisidine‐co‐o‐toluidine) thin films was investigated. Homopolymer and copolymer thin films were synthesized electrochemically, under cyclic voltammetry conditions, in aqueous solutions of inorganic acids (H₂SO₄, HCl, HNO₃, H₃PO₄, and HClO₄) and organic acids (benzoic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, and adipic acid) at room temperature. The films were characterized by cyclic voltammetry, ultraviolet–visible spectroscopy, and conductivity measurements with a four‐probe technique. The ultraviolet–visible spectra were obtained ex situ in dimethyl sulfoxide. The optical absorption spectra indicated that the formation of the conducting emeraldine salt (ES) phase took place in all the inorganic electrolytes used, whereas in organic acid supporting electrolytes, ES formed only with oxalic acid. Moreover, the current density and conductivity of the thin films was greatly affected by the nature and size of the anion present in the electrolyte. For the copolymer, the conductivity lay between the conductivity of the homopolymers, regardless of the supporting electrolyte used. The formation of the copolymer was also confirmed with differential scanning colorimetry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2634–2642, 2003     

Copolymers of aniline and o‐methoxyaniline: Synthesis and characterization

High‐conversion (HC) copolymers of aniline and o‐methoxyaniline (o‐anizidine) were synthesized for the first time by chemical oxidative copolymerization using various polymerization techniques (simultaneous or consecutive introduction of comonomers into the polymerizing system). Low‐conversion (LC) copolymers have also been synthesized for comparison. The polymers obtained were characterized using ¹H‐NMR, infrared, and electronic absorption spectroscopy, differential scanning calorimetry, and electrical conductivity measurements. Solubility characteristics and composition of different fractions of the copolymers were also determined. It was shown that in contrast to the LC copolymers, HC copolymers reveal relatively poor solubility. Electrical conductivity of copolymers and also of o‐methoxyaniline homopolymer is lower compared to polyaniline, which correlates with notable hypsochromic (blue) shift of the bands in electronic absorption spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 75–81, 2006     

Copolymers of aniline and o‐methoxyaniline: Synthesis and characterization

High‐conversion (HC) copolymers of aniline and o‐methoxyaniline (o‐anizidine) were synthesized for the first time by chemical oxidative copolymerization by using various polymerization techniques (simultaneous or consecutive introduction of comonomers into the polymerizing system). Low‐conversion (LC) copolymers have also been synthesized for comparison. The polymers obtained were characterized by using ¹H‐NMR, infrared, and electronic absorption spectroscopy; differential scanning calorimetry; and electrical conductivity measurements. Solubility characteristics and composition of different fractions of the copolymers were also determined. It was shown that, in contrast to the LC copolymers, HC copolymers reveal relatively poor solubility. Electrical conductivity of copolymers and also of o‐methoxyaniline homopolymer is lower as compared to polyaniline, which correlates with notable hypsochromic (blue) shift of the bands in electronic absorption spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1822–1828, 2005     

Copolymers of aniline with o‐ and m‐toluidine: synthesis and characterization

Copolymers of aniline and toluidine were synthesized by oxidative chemical polymerization using different ratios of the monomers in the feed, and characterized by a number of techniques including UV–visible, IR, Raman, ¹H NMR and EPR spectroscopies, as well as by thermogravimetric analysis and conductivity measurements. The properties of the copolymers are influenced by the amount of toluidine in the copolymer. Poly(o‐toluidine) and poly(m‐toluidine) are noticeably different in their solubility and conductivity. The copolymers show better solubilities than polyaniline but have lower conductivities. Differences in the properties of the salt and base forms of the copolymers are pointed out. Copyright © 2003 Society of Chemical Industry     

Corrosion protective bi‐layered composites of polyaniline and poly(o‐anisidine) on low carbon steel

Bi‐layered composites of polyaniline (PANI) and poly(o‐anisidine) (POA) were investigated for corrosion protection of low carbon steel (LCS). In this work, homopolymers and bi‐layers of PANI and POA were electropolymerized on LCS from an aqueous salicylate solution by using cyclic voltammetry. These coatings were characterized by cyclic voltammetry, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). Corrosion tests were carried out in aqueous 3% NaCl solution for LCS coated with PANI, POA, bi‐layered POA/PANI (POA on top of the PANI) or PANI/POA (PANI on top of the POA) composites using open circuit potential (OCP) measurements, potentiodynamic polarization technique, and electrochemical impedance spectroscopy (EIS). The single layer of PANI and POA protected the LCS in 3% NaCl for 8 and 16 h, respectively. The bi‐layered composite coatings provide effective protection to LCS for a longer time than a single layered PANI or POA coating. However, the corrosion protection offered to LCS depends on the deposition order of polymer layers in the composite. The PANI/POA composite provides better protection to LCS against corrosion than POA/PANI coating. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparison of poly(o‐anisidine) and poly(o‐anisidine‐co‐aniline) copolymer synthesized by chemical oxidative method

In this study, poly(o‐anisidine) [POA], poly(o‐anisidine‐co‐aniline) [POA‐co‐A], and polyaniline [PANi] were chemically synthesized using a single polymerization process with aniline and o‐anisidine as the respective monomers. During the polymerization process, p‐toluene sulfonic acid monohydrate was used as a dopant while ammonium persulfate was used as an oxidant. N‐methyl‐pyrolidone (NMP) was used as a solvent. We observed that the ATR spectra of POA‐co‐A showed features similar to those of PANi and POA as well as additional ones. POA‐co‐A also achieved broader and more extended UV–vis absorption than POA but less than PANi. The chemical and electronic structure of the product of polymerization was studied using Attenuated Total Reflectance spectroscopy (ATR) and UV–visible spectroscopy (UV–vis). The transition temperature of the homopolymers and copolymers was studied using differential scanning calorimetry and the viscosity average molecular weight was studied by using dilute solution viscometry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Water‐soluble copolymers from functionalized monomers (sodium o‐ and p‐methacryloylaminophenylarsonate): Synthesis and characterization

Copolymers of sodium o‐methacryloylaminophenylarsonate (o‐MAPHA‐Na) 1 and p‐methacrylolylaminophenylarsonate (p‐MAPHA‐Na) 2 with sodium acrylate (AA‐Na) 3 , sodium methacrylate (AM‐Na) 4 and acrylamide (AAD) 5 were prepared by free radical polymerization in aqueous media at 70°C using potassium persulfate (K₂S₂O₈) as the initiator. The total monomer concentration was carried out at 0.5M and the feed ratio ( M₁ : M₂ ) was varied from 10 : 90 to 90 : 10 mol%. The kinetic study was carried out by dilatometric method. The copolymer compositions were calculated by arsenic content in the copolymers. The As content (ppm) was determined by atomic absorption spectrometry (AAS). The reactivity ratios (r₁, r₂) were estimated by the Kelen‐Tüdös linearization method as well as error‐in‐variables method using the computer program RREVM®. In all cases, r₁ < 1 and r₂ > 1, indicating a tendency to form random copolymers. The values suggest that the copolymers contain a larger proportion of comonomer (i.e., AA‐Na, AM‐Na, or AAD). Weight‐average molar masses (M _w) of copolymers were determined by multi‐angle light scattering. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of poly(o‐anisidine)/V2O5 and poly(o‐anthranilic acid)/V2O5 nanocomposites

Poly(o‐anisidine)/V₂O₅ and poly(o‐anthranilic acid)/V₂O₅ nanocomposites were prepared by in situ intercalative polymerization, and the structure and electrical properties of these nanocomposites were investigated using GPC, TGA, XRD, TEM, FTIR, UV‐vis as well as conductivity measurement. The results show that the steric effect and nature of the substituting groups in the aromatic ring has an influence on the structure and electrical properties of the nanocomposites. Poly(o‐anisidine) or poly(o‐anthranilic acid) exists as a monolayer of outstretched chains in the gallery of the V₂O₅ xerogel owing to the confined environment in the nanometer‐size gallery. And intercalation of poly(o‐anisidine) or poly(o‐anthranilic acid) can improve the conductivity of V₂O₅ xerogel. Copyright © 2005 Society of Chemical Industry     

Copolymerization of poly(1‐naphthylamine) with aniline and o‐toluidine

The commercial use of polyaniline has been impeded by its intractable nature and insolubility. The use of substituted polyaniline has been attempted mainly to increase the processibility of polyaniline, but this approach usually results in the lowering of the conductivity. This study reports the synthesis of poly(1‐naphthylamine), a fused ring derivative of polyaniline, and its copolymers with aniline and o‐toluidine via a chemical polymerization method. Spectral, thermal, morphological, and conductivity studies were carried out to elucidate the influence of the incorporation of aniline and o‐toluidine units into poly(1‐naphthylamine). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrochemical polymerization of fluoro‐ and chloro‐substituted anilines and copolymers with aniline

Poly(2‐fluroaniline) and poly(2‐chloroaniline) were synthesized by an electrochemical method in an acetonitrile solution containing tetrabutylammonium perchlorate and perchloric acid. Also, the electrochemical copolymerization of aniline with 2‐fluroaniline and 2‐chloroaniline was carried out in the same medium. Cyclic voltammograms of the deposited films were recorded in neutral, acidic, and basic solutions. The electrochemical behavior of the films showed the same characteristic results as conventional polyaniline. The observed decrease in the dry electrical conductivity of the copolymers with respect to polyaniline was attributed to the incorporation of the fluoro‐ and chloro‐substituted anilines into the polyaniline chain. Further characterization of the polymer and copolymer products was performed through dry electrical conductivity measurements, ultraviolet–visible spectroscopy, and Fourier transform infrared spectroscopy. The relative solubility of the films was determined in various common organic solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2302–2312, 2004     

Synthesis,characterization, and comparison of self‐doped,doped, and undoped forms of polyaniline,poly(o‐anisidine), and poly[aniline‐co‐(o‐anisidine)]

Polyaniline (PANI), poly(o‐anisidine), and poly[aniline‐co‐(o‐anisidine)] were synthesized by chemical oxidative polymerization with ammonium persulfate as an oxidizing reagent in an HCl medium. The viscosities, electrical conductivity, and crystallinity of the resulting polymers (self‐doped forms) were compared with those of the doped and undoped forms. The self‐doped, doped, and undoped forms of these polymers were characterized with infrared spectroscopy, ultraviolet–visible spectroscopy, and a four‐point‐probe conductivity method. X‐ray diffraction characterization revealed the crystalline nature of the polymers. The observed decrease in the conductivity of the copolymer and poly(o‐anisidine) with respect to PANI was attributed to the incorporation of the methoxy moieties into the PANI chain. The homopolymers attained conductivity in the range of 3.97 × 10^?3 to 7.8 S/cm after doping with HCl. The conductivity of the undoped forms of the poly[aniline‐co‐(o‐anisidine)] and poly(o‐anisidine) was observed to be lower than 10^?5 J/S cm^?1. The conductivity of the studied polymer forms decreased by the doping process in the following order: self‐doped → doped → undoped. The conductivity of the studied polymers decreased by the monomer species in the following order: PANI → poly[aniline‐co‐(o‐anisidine)] → poly(o‐anisidine). All the polymer samples were largely amorphous, but with the attachment of the pendant groups of anisidine to the polymer system, the crystallinity region increased. The undoped form of poly[aniline‐co‐(o‐anisidine)] had good solubility in common organic solvents, whereas doped poly[aniline‐co‐(o‐anisidine)] was moderately crystalline and exhibited higher conductivity than the anisidine homopolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and characterization of poly(o‐ and m‐amino benzyl amine) and the copolymers with aniline. Study with Cu(II)

Poly(o‐amino benzyl amine), poly(m‐amino benzyl amine), and the copolymers with aniline were synthesized in 10^?4M HCl by using ammonium persulfate as oxidizing agent. The copolymers were synthesized at various feed mole fractions of comonomer diamine and characterized by elemental analysis, FTIR, ¹H‐NMR spectroscopy, and electrical conductivity. The polymerization yield depended on the substituent position in the aromatic ring. Copper ion was incorporated in the polymers and the amount depended on the side groups position in the aromatic ring. The thermal stability increased when copper ions and aniline units were incorporated in the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 31–36, 2004     

Synthesis and characterization of conducting poly(aniline‐co‐diaminodiphenylsulfone) copolymers

Polyaniline, poly(aniline‐co‐4,4′‐diaminodiphenylsulfone), and poly(4,4′‐diaminodiphenylsulfone) were synthesized by ammonium peroxydisulfate oxidation and characterized by a number of techniques, including infrared spectroscopy, ultraviolet–visible absorption spectroscopy, ¹H‐NMR, thermogravimetric analysis, and differential scanning calorimetry. These copolymers had enhanced solubility in common organic solvents in comparison with polyaniline. The conductivities of the HCl‐doped polymers ranged from 1 S cm^?1 for polyaniline to 10^?8 S cm^?1 for poly(4,4′‐diaminodiphenylsulfone). The copolymer compositions showed that block copolymers of 4,4′‐diaminodiphenylsulfone (r₁ > 1) and aniline (r₂ < 1) formed and that the reactivity of 4,4′‐diaminodiphenylsulfone was greater than that of aniline. The results were explained by the effect of the ? SO₂? group present in the polymer structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2337–2347, 2003     

Synthesis and characterization of electrically conducting copolymers based on biphenyl and thiophene

New electrically conducting copolymers based on biphenyl and thiophene in a form of film were synthesized by electropolymerization using potentiostatic conditions and the corresponding homopolymers, polyphenylenes, and polythiophenes, for comparison reasons. Different values of applied potential were used, to study its effect on the structure, morphology, and electrical conductivity of the films. From the analysis of the current‐time curves, it was found that the growth of the films follows layer by layer (2D) mechanism. The films were studied by FTIR, TGA, XRD, SEM‐EDAX and their electrical conductivity was determined, as well as their energy gap (E_g) by cyclic voltammetry. The copolymers had higher conductivity (appr. 1 S/cm) and lower E_g (appr. 1.2 eV) than that of the corresponding homopolymers. These materials due to their high conductivity, high stability under repetitive potential cycling, and partial solubility are candidates for electronic applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of aniline and o‐toluidine conducting copolymer microtubes with the template‐synthesis method

Copolymer microtubes composed of aniline and o‐toluidine were prepared through the synthesis of the desired polymer within the pores of a microporous anodic aluminum oxide (AAO) template. Scanning electron microscopy and transmission electron microscopy revealed that the obtained copolymer microtubes had uniform and well‐aligned arrays, and the aspect ratios of the AAO membranes could be controlled through their diameter and length. Infrared spectrometry and X‐ray photoelectron spectroscopy supported the surface analysis for the microtubes and also proved the formation of copolymers. Ultraviolet–visible/near‐infrared spectra proved that the doping effect decreased with an increase of o‐toluidine in the copolymers, but the solubility greatly improved (up to 3.83 g/L in N,N‐dimethylformamide), and the conductivity was as high as approximately 17.4 S cm^?1. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1539–1543, 2005     

Synthesis and characterization of electrically conducting copolymers based on benzene and biphenyl

Poly(p‐phenylene) (H‐PPP), which is one of the firstly investigated conducting polymer, has the disadvantage of difficult processability because it is infusible and insoluble. The use of biphenyl instead of benzene leads to ortho‐, meta‐, para‐polyphenylenes (H‐PP) which are more soluble and easier to be processed, however their electrical conductivity is lower. Copolymers of polyphenylenes (C₁ and C₂) and corresponding homopolymers (H‐PPP and H‐PP) were produced by the oxidative cationic polymerization of benzene and/or biphenyl. The soluble (‐S) and the insoluble (‐I) in chlorobenzene polyphenylenes were separated (H‐PP‐I, H‐PP‐S, C₁‐I, C₁‐S, C₂‐I, and C₂‐S) and they were doped with a solution of FeCl₃. All polyphenylenes were studied by FTIR, XRD, TGA, and their electrical conductivity with constant current was determined. Pronounced differences between the copolymers and the homopolymers were observed, indicating the different structure of the former. The values of the electrical conductivity of doped insoluble copolymers (10^?4 and 10^?5 S/cm) are between that of H‐PPP (10^?3 S/cm) and H‐PP‐I (10^?6 S/cm). The values of the electrical conductivity of doped soluble copolymers (10^?5 S/cm) are considerably higher than that of H‐PP‐S (10^?9 S/cm). The new electrically conductive polyphenylenes that were produced differ significantly from the corresponding homopolymers and combine good electrical conductivity and solubility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of temperature‐responsive poly(vinyl alcohol)‐based copolymers

A poly(vinyl alcohol) (PVA)/sodium acrylate (AANa) copolymer was synthesized to improve the water solubility of PVA at the ambient temperature. Furthermore, a series of temperature‐responsive acetalyzed poly(vinyl alcohol) (APVA)‐co‐AANa samples of various chain lengths, degrees of acetalysis (DAs), and comonomer contents were prepared via an acid‐catalysis process. Fourier transform infrared and ¹H‐NMR techniques were used to analyze the compositions of the copolymers. The measurement of the turbidity change for APVA‐co‐AANa aqueous solutions at different temperatures revealed that the lower critical solution temperature (LCST) of the copolymers could be tailored through the control of the molecular weight of the starting PVA‐co‐AANa, DA, and comonomer ratios. Lower LCSTs were observed for APVA‐co‐AANa with a longer chain length, a higher DA, and fewer acrylic acid segments. In addition, the LCSTs of the APVA‐co‐AANa aqueous solutions appeared to be salt‐sensitive. The LCSTs decreased as the concentration of NaCl increased. Moreover, atomic force microscopy images of APVA‐co‐AANa around the LCST also proved the temperature sensitivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrochemical synthesis and characterization of conducting copolymers of biphenyl with pyrrole

Copolymer films of biphenyl and pyrrole were synthesized by electrochemical polymerization. The influence of the applied potential used for the electropolymerization on the structure, morphology, electrical conductivity, and stability of the films was examined. From the analysis of the current–time curves, it was found that the growth of the copolymer films starts immediately. The films were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis, X-ray diffraction analysis, and scanning electron microscopy–energy-dispersive X-ray analysis, and their electrical conductivity (σ), energy gap (E_g), and electrochemical stability were also determined. Based on the results, the copolymers were classified into three groups. The first includes the (PP-PPy)_0.80 copolymer synthesized at the lowest potential E_ox (0.80 V), having the highest ratio R (R = 0.35) of quinoid to benzenoid rings (calculated from FTIR), the highest value of σ (σ = 0.9 S/cm), the lowest E_g (E_g = 1.20 eV), and has compact morphology. The second group concerns the copolymers synthesized at higher potential (0.82 up to 0.86 V), having lower R (∼ 0.20), lower σ (below 0.4 S/cm), higher E_g (∼ 1.35 eV), and they are less compact with many pores. The third group includes the copolymers synthesized at even higher applied potential (0.88 and 0.90 V), having even lower R values (∼ 0.10), significantly lower σ (∼ 10⁻³ S/cm), even higher E_g (∼ 1.70 eV), and they are very porous. The applied potential during electropolymerization strongly affects the properties of the synthesized copolymers. Because of the combination of high conductivity, low energy gap, and partial solubility with significant electrochemical stability, these new copolymers are attractive candidates for many applications. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New conducting thermoplastic elastomers. I. Synthesis and chemical characterization

In the last 20 years, much interest has been focused on conducting polymers to find new materials to transfer from research to industry. However, in many cases, as for elastomers for which intrinsically conducting materials are unavailable, it is necessary to use conducting particles that are physically mixed with the polymeric matrix to give loaded rubbers. In this work we report the synthesis and the chemical characterization of an intrinsically conducting material with good mechanical and electrical conduction properties. To achieve such a global goal, we covalently linked, by an amidation reaction, the terminal NH₂ of Emeraldine (EB) and sulfonated Emeraldine (SPAN) to a free carboxylic group belonging to the repetitive unit of a functionalized segmented polyurethane. The reaction was carried out by activating such a carboxylic group with N,N′‐dicyclohexylcarbodiimide and N‐hydroxysuccinimide. The reaction yields and the chemical properties of the polymers were studied by proton and carbon‐13 nuclear magnetic resonance, ultraviolet, and Fourier transform infrared spectroscopy. The average numbers of EB or SPAN aromatic rings per polyether urethane acid (PEUA) repetitive unit, which cannot be assumed to be amidation degree because at this moment the molecular weights of the inserted EB and SPAN chains are unavailable, were 6 in case of the polymer obtained from the pristine Emeraldine and 1 for that obtained from the sulfonated Emeraldine. This result could be because SPAN was used in the acidic form, which depresses the nucleophilicity of the NH₂ group because of the presence of the sulfonic protons. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 857–867, 2002     

Synthesis and humidity sensitivity of conducting polyaniline in SBA‐15

Conducting polyaniline (PANI) was synthesized in mesoporous silica SBA‐15. The investigations of XRD, N₂ adsorption–desorption, and IR spectra confirm the existence of polyaniline in the channels of SBA‐15 hosts. The impedance of PANI/SBA‐15 composites was studied at different relative humidity (RH) levels, ranging from 11 to 95% RH. The loadings of PANI as well as the concentration of HCl solution have substantial influence on the impedance values. The variation in impedance value of all PANI/SBA‐15 composites is more obvious than that of bulk PANI samples at the same RH. All these results imply that PANI/SBA‐15 composites may have better humidity‐sensitive properties than those of bulk PANI samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1597–1601, 2004