Studies on Substituted Derivatives of Polyaniline: Effect of Polymerization Conditions on Electrical Conductivity

Abstract

Polyaniline, poly(o-methoxyaniline)and poly(N-phenylaniline) were synthesized chemically under different polymerization conditions by peroxodisulphate oxidation in HCl and in a mixture of HCl and CH₃CN. The polymer prepared at 0°C, monomer-oxidant ratio 1:1.15 and a strong acidic medium, has the least bandgap and maximum electrical conductivity. The electrical conductivity depends on degree of oxidation and protonation. The bulky substituents increase the torsion angle and hence disorder causes the decrease in the electrical conductivity of polymer.     

Synthesis,Electrical, Electronic and Charge Transport Properties of Poly(aniline‐co‐p‐toluidine)

Copolymers of aniline with p‐toluidine were synthesized for different molar ratios of the respective monomers in acid medium. The electrical conductivity, charge transport and spectral characteristics upon incorporation of p‐toluidine units into the polyaniline backbone were investigated. The electrical conductivity of the copolymers showed frequency dependence which became more prominent with an increase in the number of p‐toluidine units in the polyaniline backbone. A direct relationship between the frequency dependence and electron localization was observed in the copolymers. Electronic spectra showed blue shifts in the π→π*and benzenoid→quinoid transitions revealing a decrease in the extent of conjugation in the copolymers. The protonated forms of the copolymers were soluble in DMSO giving polaron band around 400 nm. The decrease in electrical conductivity was attributed to the greater electron localizations as revealed from the broader ESR signals. Temperature dependence of electrical conductivity showed that charge transport was mainly through variable range hopping though a mixed conduction behavior was observed at higher temperature range.     

Synthesis,Electrical Conductivity,Spectral and Thermal Stability Studies on Poly(aniline-co-o-nitroaniline)

o-Nitroaniline units were incorporated in the polyaniline backbone through copolymerization with aniline. The copolymers were synthesized for 1:3 and 1:1 molar ratios of aniline and o-nitroaniline in acidic medium using potassium persulphate as oxidant and their properties were compared with that of polyaniline. The polymers showed less electrical conductivity than polyaniline. Unlike polyaniline, the presence of nitro group caused higher frequency dependence of electrical conductivity. Electronic spectra showed a blue shift in both the band of the copolymers due to the decrease in the extent of conjugation leading to lower conductivity, which could also be explained in terms of a decrease of delocalization of electron as evinced from electron para magnetic resonance (EPR) data. Thermo gravimetric analysis (TGA) revealed that copolymer derived from 1:1 molar ratio showed comparable thermal stability with polyaniline and the one derived from 1:3 molar ratios is thermally less stable than polyaniline. Activation energies for thermal degradation were estimated using Broido equation. The temperature dependence of electrical conductivity suggested charge transport is mainly through variable range hopping.     

Electrochemical Polymerization of Aniline at Low Supporting-Electrolyte Concentrations and Characterization of Obtained Films

Conductive polymers of aniline were synthesized in aqueous acidic media such as perchloric, sulfuric, hydrochloric, phosphoric, and trifluoroacetic acids and the effect of supporting electrolyte was investigated. The conductivity of each polyaniline (PAn) sample was determined by the four-probe technique. PAn (H₂SO₄) sample was shown to have the highest conductivity, specifically, 3.55 S cm^–1. The effect of concentrations of monomers and acids on the conductivity of PAn's was studied. It was observed that the conductivity decreased with increasing aniline concentration and increased with increasing sulfuric acid concentration. The conductivities of PAn (CF₃COOH) were also investigated in different supporting electrolytes and highly good increments of its conductivities were obtained. Magnetic properties of the PAn salts were analyzed by Gouy balance measurements and it was found that their conducting mechanisms are of bipolaron nature. From the FTIR analysis it was found that polymerization occurs via the –NH₂ group in a head-to-tail mechanism. The thermal analyses revealed that PAn (HCl) among the PAn salts studied shows the highest thermal stability. Surface analyses of polymers were clarified by scanning electron microscopy. From elemental analysis results, PAn salts were concluded to be in emeraldine structure.     

Properties of silicas chemically modified by monodentate amines studied by conductometry

The protonation of aminoalkyl groups covalently bonded on the silica surface was studied by the conductometric titration method. Porous varieties of silica can adsorb HCl from an aqueous solution. Conductometric titration was proposed for the determination of concentrations and constants of protolytic equilibrium of grafted amino groups. During HCl chemisorption the effect of temperature on the electric conductivity of suspensions of the modified silicas was studied. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1789–1793, August, 2005.     

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.     

固相法合成苯胺与邻甲氧基苯胺共聚物及其性能

以苯胺和邻甲氧基苯胺为单体,甲磺酸为掺杂酸,用固相法合成了甲磺酸掺杂苯胺与邻甲氧基苯胺共聚物。 通过红外光谱、紫外可见吸收光谱、X射线衍射、透射电子显微镜、循环伏安和电导率等对共聚物进行了结构表征和性能测试。 结果表明,不同摩尔比的苯胺与邻甲氧基苯胺共聚物处于中间氧化态,随邻甲氧基苯胺含量的增大,共聚物的掺杂率降低。 共聚物具有较高的结晶性和纤维状形貌,当苯胺与邻甲氧基苯胺摩尔比为1∶1时,具有较高的电化学活性,其导电率为1.65 S/cm。     

Reactive sensing capability towards the working electrical and chemical conditions of poly (aniline –co–o-toluidine) copolymers

Conducting polymers are considered as reactive gels which can sense the working ambient through their unique electrochemical reaction. Copolymers of aniline with o-toluidine for three different monomer compositions were synthesized chemically and were characterized using FTIR and UV-Vis spectroscopy, SEM, TGA, and cyclic voltammetry. The electrochemical reactive sensing characteristics with respect to the electrical and chemical working conditions of the copolymers were verified and compared through Chronopotentiometric responses in aqueous solutions of HCl by changing the reaction variables: applied current and chemical environment (electrolyte concentration) at a fixed constant charge. The consumed electrical energy during the electrochemical reaction of the copolymers varies linearly with the driving current and follows a logarithmic dependence on the electrolyte concentration. The consumed electrical energy during the reaction was found to act as the sensing parameter. At the same experimental condition, the sensitivity was associated with the conductivity of the copolymers. The highly conducting composition gives the highest sensitivity. These experimental results were fitted with the theoretical equation.

     

Chemical synthesis and characterization of poly(aniline‐co‐ethyl 3‐aminobenzoate) copolymers

Copolymers of aniline and ethyl 3‐aminobenzoate (3EAB) were synthesized by chemical polymerization in several mole ratios of aniline to functionalized aniline, and their physicochemical properties were compared to those of poly(aniline‐co‐3‐aminobenzoic acid) (3ABAPANI) copolymers. The copolymers were characterized with UV–vis, FTIR, Raman, SEM, EPR, and solid‐state NMR spectroscopy, elemental analysis, and conductivity measurements. The influence of the carboxylic acid and ester group ring substituents on the copolymers was investigated. The spectroscopic studies confirmed incorporation of 3ABA or 3EAB units in the copolymers and hence the presence of C?O group in the copolymer chains. The conductivity and EPR signals both decreased with increasing 3EAB content of the copolymers emeraldine salt (ES) form. The conductivity of the ES form of 3ABAPANI was found to be high (1.4 × 10^?1 S cm^?1) compared with the conductivity (10^?2–10^?3 S cm^?1) of 3EABPANI (ES) copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1339–1347, 2010     

Effect of aromatic substitution in aniline on the properties of polyaniline

Substitution in aniline has tremendous effect in the synthesis of poly(substituted anilines) as well as in their properties. In this investigation polyaniline (PANI), poly(m-nitro aniline) (PMNA), poly(m-amino phenol) (PMAP) and poly(o-ethyl aniline) (POEA) were synthesized by oxidative polymerization under identical conditions. Different properties were measured and compared with PANI to find out the presence of electron donating -OH group, electron withdrawing -NO₂ group and less effecting ethyl group on the properties of poly(substituted anilines). It was found that presence of any type of substitution in the benzene ring of aniline increases the solubility of the resulted polymer but reduces the yield, degree of polymerization, thermal stability, electrical and thermal conductivity. The colors, bulk density, particle size, percentage of crystallinity vary considerably depending on the nature of substitution.     

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 and properties of fullerene-containing N-vinylpyrrolidone copolymers

Branched copolymers containing covalently bonded fullerene C₆₀ were synthesized by cross-linking radical copolymerization of N-vinylpyrrolidone with triethylene glycol dimethacrylate in toluene saturated with fullerene. Their composition was studied by elemental analysis and IR and electronic absorption spectroscopy. The concentration of double bonds, characteristic viscosity, and glass-transition temperature of the fullerene-containing copolymers were determined by ozonoliysis, viscosimetry, and differential scanning calorimetry. The parameters and thermal stability of the fullerene-containing copolymers were compared with those of their non-functionalized analogs.     

Synthesis of a water‐soluble diblock copolymer of polysulfonic diphenyl aniline and poly(ethylene oxide)

We report the synthesis of a water‐soluble diblock copolymer composed of polysulfonic diphenyl aniline (PSDA) and poly(ethylene oxide) (PEO), which was prepared by reacting an amine‐terminated PSDA and tosylate PEO (PEO‐Tos). First, a HCl‐mediated polymerization of sulfonic diphenyl aniline monomer with the formation of HCl‐doped PSDA was carried out. After its neutralization and reduction, a secondary amine‐functionalized PSDA was obtained. Second, PEO‐Tos was synthesized via the tosylation of the monohydroxyl PEO methyl ether with tosylol chloride. Diblock copolymers with various PEO segment lengths (PSDA‐b‐PEO‐350 and PSDA‐b‐PEO‐2000) were obtained with PEO‐350 [number‐average molecular weight (M_n) = 350] and PEO‐2000 (M_n = 2000). The prepolymers and diblock copolymers were characterized by Fourier transform infrared spectroscopy, NMR, mass spectrometry, and ultraviolet–visible light. They had relatively low conductivities, ranging from 10^?6 to 10^?3 S/cm, because of the withdrawing effect of the sulfonic group as well as the steric effects of the bulky aromatic substitutuents at the N sites of the polyaniline backbone and of the PEO block. These polymers were self‐doped, and an intermolecular self‐doping was suggested. The external doping was, however, more effective. The self‐doping induced aggregation in water among the PSDA backbones, which was also stimulated by the presence of hydrophilic PEO blocks. Furthermore, the electrical conductivities of the diblock copolymers were strongly temperature‐dependent. PSDA‐b‐PEO‐2000 exhibited about one order of magnitude increase in conductivity upon heating from 32 to 57 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2179–2191, 2004     

Metal Complexes of Aniline: Infrared and Raman Spectra

Abstract

The literature for the years 1965–1987 has been searched for all significant papers which refer to the vibrational spectra of metal complexes of aniline and substituted anilines. These papers have been reviewed with particular reference to isotopic labelling and metal ion substitution studies as assignment techniques and to the structural and bonding information which can be derived from the spectra. Compounds of the following classes are included: [M(an)₂X₂] (M = Mn, Co, Ni, Cu, Zn, Cd, Hg; an = aniline, X - Cl, Br, I, NCS); cis- and trans-[Pt(an)₂X₂] (X = Cl, Br, I, NO₂); [M(R-an)₂X₂] (M = Mn, Co, Ni, Cu, Zn; R-an = o-, m- and p-toluidine and other substituted anilines; X = Cl, Br, I); aniline adducts of metal β-ketoenolates; the complexes trans-[PtL(R-an)X₂] (L = CH₂?CH₂ or CO, R-an = aniline or a substtuted aniline, X = Cl, Br); and other miscellaneous systems comprising aniline as a ligand.     

Conducting films of poly(aniline‐co‐1‐amino‐ 2‐naphthol‐4‐sulfonic acid) blended with LDPE for its application as antistatic encapsulation material

The paper presents the electrostatic charge dissipative (ESD) properties of the conducting copolymers of aniline (AN) and 1‐amino‐2‐naphthol‐4‐sulfonic acid (ANSA) blended with low‐density polyethylene (LDPE). The copolymers of aniline and ANSA were synthesized under different reaction conditions. Blending of copolymers with LDPE was carried out in twin screw extruder by melt blending method by loading 0.5 and 1.0 wt% of the conducting copolymer in LDPE matrix. The mechanical properties of the blended films depend on the incorporation of copolymer in the LDPE matrix. The morphology of copolymer–LDPE blend was studied by scanning electron microscopy. The conductivity of the blown film of poly(AN‐co‐ANSA)/LDPE blend was found to be in the range of 10^?6–10^?11 S/cm, showing its potential use as antistatic bag for the encapsulation of electronic equipments. The static decay time of the film was found to be of the order of 0.1–1.9 sec on recording the decay time from 5000 to 500 V. Static charge measurements carried out on the films show that no charge is present on the surface. The level of interaction between the copolymers and the matrix polymer was determined by the FTIR spectra, blend morphology, electrical conductivity, and thermal analysis. The effect of the morphology on electrical and antistatic behavior of copolymers has also been investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

Sonochemical synthetic methods to produce functionalized conducting copolymers

Polyaniline (PANI) is one of the most investigated intrinsically conducting polymers. Copolymerization of aniline with aniline derivatives was considered one of the most effective and promising ways of improving the properties of PANI. In this work, firstly ethyl 3‐aminobenzoate and butyl 3‐aminobenzoate were synthesized from 3‐aminobenzoic acid by direct esterification. Then the copolymerization of 3‐amino benzoic acid, ethyl 3‐aminobenzoate, and butyl 3‐aminobenzoate with aniline was carried out by sonochemical polymerization in aqueous hydrochloric acid using ammonium persulfate (APS) as an initiator. The effects of variation in the molar ratio of the two monomers on chain structure, conductivity, and the redox properties of the copolymer are discussed. The prepared polymers are characterized by ¹H NMR spectroscopy, X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT‐IR). Thermal behavior of the prepared copolymers was studied by differential scanning calorimetry. The copolymers were doped with HCl and their conductivity was measured. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis,structure characterization,and gas sensitive properties of a copolymer of aniline with phenol

A new kind of conductive copolymers of aniline with phenol was designed and synthesized by using oxidation polymerization and the results showed that the apparent inherent conductivities of the copolymers are in the range of 10^?2 to 10^?10 S/cm which covers from conductors to insulators. The results showed that the conductivity of the copolymers strongly depends on synthesis conditions, such as reaction time, molar ratios of oxidizer to monomers and aniline to phenol, concentrations of reactants, and reaction temperature. Compared to the conventional (co)polymers of aniline and its derivatives, the magnitudes of the reversible conductivity changes are very significant, about two orders, and get to the maximum readings in about 5 min when they are exposed to ammonia gas, hydrochloric acid gas, and a various vapors of organic compounds, such as methanol, alcohol, acetone, benzene, toluene, chloroform, carbon tetrachloride, etc. It should be noted that with the introduction of the weak acidic structural units into the polyaniline chains, the copolymers are reversibly responded to both acidic and basic gases promptly. Copyright © 2009 John Wiley & Sons, Ltd.     

具有电活性苯胺四聚体接枝聚谷氨酸的合成与表征

以N-羟基琥珀酰亚胺(NHS)活化聚L-谷氨酸的羧基并与苯胺四聚体的氨基缩合,得到了以可生物降解的聚谷氨酸为主链,具有电活性的苯胺四聚体为侧链的新型接枝聚合物.用1H-NMR、质谱分析、光谱分析的方法确定了化合物的结构.侧链羧基的存在使聚合物可以溶解于碱性的缓冲溶液中.对聚合物的电化学性质进行了紫外及循环伏安的表征,研究结果表明,接枝后的聚合物具有与苯胺低聚体相似的可逆的氧化还原过程并可被质子酸掺杂,表现出良好的电化学活性.同时,以定量紫外吸收及元素分析的方法分别测定了聚合物的接枝率.实验中通过控制反应的投料比可以使苯胺四聚体的接枝率达到40%以上,并对聚合物的自掺杂现象进行了讨论.     

A comparative study on the structural changes in leucoemeraldine and emeraldine base upon doping by perchlorate

The changes in the structure of leucoemeraldine (LM) and emeraldine (EM) base upon doping by perchlorate anions are studied by X-ray photoelectron spectroscopy (XPS) and infrared (IR) absorption spectroscopy. In the case of LM, interactions of the amine nitrogens with the perchlorate anions result in a nitrogenonium ion structure analogous to that arising from the protonation of imine nitrogens in EM by HCl except the chloride anion in the latter has been replaced by the perchlorate anion. A small amount of partially ionic and covalent chlorine is also incorporated in the LM–perchlorate complexes. The maximum electrical conductivity that is achieved in these complexes is about 4 S/cm. In contrast, the maximum conductivity of the EM–perchlorate complexes is three orders of magnitude lower. The interactions of perchlorate anions with EM base result in the preferential disappearance of the imine units over the amine units.     

Synthesis and physicochemical properties of copolymers of aniline and 3,4-ethylenedioxythiophene

Copolymers of various compositions have been synthesized via copolymerization of aniline with 3,4-ethylenedioxythiophene in the presence of a poly(4-styrenesulfonic acid) matrix, and a mechanism of copolymerization has been suggested. It has been shown that the synthesized copolymers are included in non-stoichiometric interpolyelectrolyte complexes with matrices stabilized by salt bonds and nonionic interactions. The copolymers of aniline and ethylenedioxythiophene possess electrical conductivity and can enter into redox and acid-base reactions.