Electrochemical and chemical synthesis of nanostructure copoly(aniline-o-anisidine-o-toluidine) and study of its electrochemical behavior in organic sulfonic acid media

Terpolymerization of aniline, o-anisidine and o-toluidine was carried out by electrochemical and interfacial chemical polymerization. All homopolymers and terpolymer thin films have been synthesized through electropolymerization at room temperature in aqueous solutions containing 0.5 M of organic sulfonic acid, such as p-toluene sulfonic acid, methane sulfonic acid, sulfosalicylic acid, dodecylbenzene sulfonic acid, and 0.1 M of aniline, o-anisidine and o-toluidine monomers, using cyclic voltammetry method, applying a sequential linear potential scan at a rate of 25 mV s^?1 between ?0.1 and 0.9 V. The electrochemical terpolymerization has been performed at various mole ratios of monomers. Nanoparticles obtained from conjugation of homo- and terpolymer with organic sulfonic acids, were prepared by a chemical oxidation via interfacial chemical polymerization. SEM micrographs, FTIR spectra and conductivity measurements using four-probe method were applied for the characterization of the products. Terpolymer was characterized by higher conductivity than poly-o-toluidine and lesser than polyaniline and poly-o-anisidine. The solubility of terpolymers was dependent on the monomers mole ratio.     

Enzymatic synthesis and characterization of a water-soluble, conducting poly(o-toluidine)

An enzymatic method for the synthesis of a water-soluble, conducting poly(o-toluidine) (POT) in the presence of sulfonated polystyrene (SPS) is presented. The enzyme horseradish peroxidase was used to polymerize o-toluidine to form a water-soluble, conducting POT/SPS complex, which exhibits moderate electrical conductivity. The synthesis is simple and the conditions are mild. The polymerization may be carried out at room temperature in pH 4.3 buffered aqueous solution with stoichiometric amount of monomer, SPS, hydrogen peroxide and catalytic amount of enzyme. The UV-Vis absorption spectra of the products display a distinct absorption peak at 740 nm at pH 4.3 that indicates the formation of the conducting, emeraldine salt form of POT. The structure and electrochemical behavior of the polymer was investigated with FT-IR and cyclic voltammetry method.     

In situ synthesis of copper nanoparticles and poly(o-toluidine): A metal-polymer composite material

We report here a novel in situ synthetic method for the preparation of poly(o-toluidine) and copper nanoparticle composite material. In this experiment, o-toluidine and cupric sulfate were used as the precursor; during the reaction o-toluidine was oxidized and forms poly(o-toluidine), while on the other hand cupric sulfate gets reduced and forms copper nanoparticle. IR, UV-vis and Raman spectra provide the information on the structure of the polymer. The TEM and SEM show the size of the nanoparticles and the morphology of the polymer, respectively.     

Glucose oxidase electrodes of a terpolymer poly(aniline-co-o-anisidine-co-o-toluidine) as biosensors

A simple technique is described for constructing a glucose sensor by the entrapment of glucose oxidase (GOD) in a poly (aniline-co-o-anisidine-co-o-toluidine) [P(A-co-o-A-co-o-T)] thin films, which were electrochemically deposited on a platinum plate in phosphate and acetate buffer. The maximum current response was observed for the said electrodes at pH 5.5 and potential 0.60 V (versus Ag/AgCl). The phosphate buffer gives high stability and fast response as compared to acetate buffer in amperometric measurements.     

Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol

Several complexes of the formula trans-[Pt(Meug)(Am)Cl₂], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η²-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, ¹H NMR, ¹³C NMR and 2D NMR spectra of the complexes were recorded and analyzed.     

Mixing Behavior of Cationic Hydrotropes with Anionic Surfactant Sodium Dodecyl Sulfate

Mixing behavior of anionic surfactant sodium dodecyl sulfate (SDS) with cationic hydrotropes aniline hydrochloride (AH), o-toluidine hydrochloride (o-TH), and p-toluidine hydrochloride (p-TH) have been studied using conductivity at different temperatures. Critical micelle concentration for different mixing mole fractions, their ideal values, and different interaction parameters have been estimated. All the parameters show nonideal behavior with synergistic interactions. Thermodynamic parameters are also calculated for these systems.     

Synthesis and characterization of aniline and aniline-o-sulfonic acid copolymers

The copolymer of aniline (An) and aniline-o-sulfonic acid (AS) is synthesized by chemical oxidation polymerization. The effects of mole ratio of copolymerized monomers on chain structure, thermostability, conductivity, redox properties of copolymer are discussed. It is indicated that if more AS monomers in polymerization system the corresponding structure units will increase, but their relation isn’t linear. When An:AS = 1:1, the ratio of structure unit in copolymer is 9:1, and it is only 1:2 for copolymer with An:AS = 1:6. The measurements of conductivity and redox activity also prove that the properties of An-co-AS(1:1), (1:3), and (1:4) are similar to polyaniline due to more An units than AS. When An:AS is higher than 1:6, it shows out the properties of copolymer is similar to those of poly(aniline-o-sulfonic acid), and their redox route is different. They will transform to follow the route of LH ↔ EH ↔ P. The results of thermo-analysis indicate that the decomposition temperature of AS units is lower than An units because of the electron-withdrawing group substitution. The decomposition temperature of polymer is related to dopant and doping degree. Electron-withdrawing group, -SO₃H, substitution and HCl doping will decrease polymer chain decomposition temperature. The mechanism of copolymerization of An and AS is different from homopolymerization. The monomer with low oxidation potential forms free radical cation firstly, which transfers to monomer with higher oxidation potential and initiates its polymerization.     

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, Characterization, and Conductivity Studies of Poly-o-Methoxyaniline Intercalated into V2O5 Xerogel

In this work we study the conductivity properties of poly-o-methoxyaniline/V₂O₅ intercalation compounds obtained through intercalative polymerization of o-methoxyaniline with V₂O₅·nH₂O in hydrogel form and by reacting directly with V₂O₅ film in de-hydrated form (xerogel). These new compounds were characterized using Fourier-transform infrared and ultra-violet/visible spectroscopies, electron paramagnetic resonance, elemental analysis (C, N, H), thermogravimetric analysis, scanning electron microscopy, dc-conductivity and powder X-ray diffraction. For samples formed from V₂O₅ xerogel in film form, an increase in dc-conductivity and a decrease in the thermal activation energy in comparison with pure matrix was observed. The increase in conductivity is attributed to an increase of carrier density in the vanadium oxide lattice and the contribution of polarons from the polymer. On the other hand, for the intercalation compound obtained with V₂O₅·nH₂O in hydrogel form presents a very low room temperature conductivity value. The decrease in conductivity is due to the lack of connectivity of the various parts that compose the material.     

Chemical oxidative polymerization of m-phenylenediamine and its derivatives using aluminium triflate as a co-catalyst

Aromatic diamine monomers, including m-phenylenediamine (mPD), 2-methyl-m-phenylenediamine (2Me-mPD), 4-methyl-m-phenylenediamine (4Me-mPD) and trimethyl-m-phenylenediamine (tMe-mPD), were polymerized by chemical oxidation using ammonium persulfate as an oxidant. Aluminium triflate (Al(OTf)₃) was also used for the first time as a co-catalyst under various polymerization conditions. The polymerization yield was improved when Al(OTf)₃ was introduced to the polymerization reaction for most polymers. The poly(2-methyl-m-phenylenediamine) (P(2Me-mPD)), poly(4-methyl-m-phenylenediamine) (P(4Me-mPD)) and poly(trimethyl-m-phenylenediamine) (P(tMe-mPD)) polymers exhibited better solubility than poly(m-phenylenediamine) (P(mPD)) polymers in most common solvents. The homopolymers obtained were characterized by FT-IR, ¹H and ¹³C NMR, WAXD and TGA. The results showed that the yield, solubility and structure of the polymers are significantly dependent on the polymerization conditions. TGA measurements indicated that the polymers have good thermal stability and decompose above 400 °C in nitrogen.     

The oxidative polymerization of p‐phenylenediamine with silver nitrate: Toward highly conducting micro/nanostructured silver/conjugated polymer composites

The oxidative polymerization of p‐phenylenediamine with silver nitrate by using various oxidant/monomer mole ratios in aqueous solutions of both acetic and nitric acid was studied experimentally and computationally. The produced micro/nanostructured conducting poly(p‐phenylenediamine)–silver composites, reaching the conductivities >10⁴ S/cm, were characterized by conductivity and density measurements, gel permeation chromatography, transmission electron microscopy, UV–visible, FTIR, and Raman spectroscopies. The highest conductivity was 31,700 S/cm for poly(p‐phenylenediamine) base–silver (81.4 wt % Ag). The unexpected increase of conductivity after deprotonation of polymer component is discussed on the basis of interfacial electrical barriers and their removal. Theoretical study of the mechanism of p‐phenylenediamine oxidation has been based on the AM1 semi‐empirical quantum chemical computations of the heat of formation of the reaction intermediates, taking into account the influence of pH and solvation effects. Quantum chemical predictions of molecular structure of poly(p‐phenylenediamine) were correlated with spectroscopic findings. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Some aspects of nitroxide-mediated living radical polymerization of N-(p-vinylbenzyl)phthalimide

The free radical polymerization of N-(p-vinylbenzyl)phthalimide (VBP) “initiated” with the adduct of 2-benzoyloxy-1-phenylethyl and TEMPO (BS-TEMPO) or TEMPO-terminated polystyrene (PS-TEMPO) in N,N-dimethylformamide (DMF) at 125 °C was found to proceed in a living fashion, providing low-polydispersity PVBP and block copolymers of the type PS-b-PVBA, where TEMPO is 2,2,6,6-tetramethylpiperidinyl-1-oxy. Unlike TEMPO-mediated styrene polymerization, the polymerization rate slightly but distinctly depended on the adduct concentration, which was interpretable as a pre-stationary behavior. The hydrolysis of those polymers gave poly(p-aminomethylstyrene) (PAMS) and PS-b-PAMS, and further treatment of the block copolymer with hydrogen chloride provided an amphiphilic block copolymer. The polymeric amphiphile was used as an emulsifier in emulsion polymerization to produce a positively charged polymeric microsphere.     

Chemical synthesis and characterization of aniline and o-anthranilic acid copolymer

The chemical co-polymerization of aniline with o-anthranilic acid (AA) to form copolymer films has been made in aqueous hydrochloric acid medium. The copolymer films were monitored by using the quartz crystal microbalance (QCM) technique. The effect of AA and its concentrations on the film formation was investigated. The results were justified by measuring the UV-Vis absorption spectra for the in situ copolymer films grown onto glass slides immersed into the polymerization media and the in situ UV-Vis absorption spectra for the copolymer in the bulk during the co-polymerization. The conductivity for the copolymer films and powder pellets at different molar ratios of aniline/AA were measured. Also, the IR spectra, X-ray diffraction and the thermal gravimetric analysis for the copolymer powder formed in the bulk in the absence and presence of AA were measured and discussed. It is found that the presence of AA affects the yield, induction period, depletion time and growth rate of the film formation. It also affects the crystallinity, and conductivity as well as the solubility of the polymer. Finally, the dopant weight fraction (w) associated with the copolymer was determined. It is almost half the value determined for the polymer in absence of AA.     

Chromaticity of poly(o-toluidine) matrix enhanced by anion-exchange mechanism

The incorporation of 9,10-anthraquinone-1,5-disulfonate (AQS₂) into the protonated form of poly(o-toluidine) (POT), produced by oxidative polymerization of the cationic form of the monomer or by doping the basic form (POT-EB) by anion-exchange has been studied by FTIR and UV-VIS spectroscopy and mass spectrometry. The presence of sulfur and the absence of chlorine proven by elemental analysis of the polymer product confirmed the substitution of the chloride anion with AQS₂ in the matrix. Molecular mechanics (MM+) calculations suggest that the optimal geometric structure (OMG) of AQS₂-doped POT is at least three (3.92) times more stable than that of the parent chloride-doped POT (HCl-doped POT). The increase of the absorbance at about 840 nm associated with the increasing concentration of AQS₂ revealed the insertion of AQS₂ into the POT chain. This observation could be explained by the diffusion of AQS₂ in the polymer chain. Kinetic parameters of the oxidative polymerization of the cationic form of o-toluidine (o-T-HClO₄) in the presence of different amounts of AQS₂ were deduced on the basis of absorbance variations. The results of computer-oriented kinetic analysis indicate that the rate-controlling step of the o-T polymerization is governed by the Ginstling-Bronstein equation representing the three-dimensional diffusion (D4). Activation parameters of the oxidative polymerization of protonated o-T in the presence of varying amount of AQS₂ were computed and discussed.     

A new approach to prepare high molecular weight poly(p-dioxanone) by chain-extending from dihydroxyl terminated propolymers

As poly(p-dioxanone) (PPDO) with a high molecular weight (viscosity-average molecular weight (M_ν) > 100,000 g/mol) is not easy to be obtained in a short time, a new approach has been developed to produce high molecular weight poly(p-dioxanone) (HPPDO-T) by chain-extending reaction of hydroxyl-terminated PPDO (HPPDO) prepolymers using toluene-2,4-diisocyanate (TDI) as chain extender. Here HPPDO prepolymers were synthesized via ring-opening polymerization of p-dioxanone (PDO) monomer initiated by 1,4-butanediol (BD) with Stannous octoate (SnOct₂) as catalyst. The resulting polymers, having a highest M_ν of 250,000 g/mol, were characterized by ¹H NMR, TG, DSC and WXRD. HPPDO prepolymers can react with TDI more effectively than the PPDO prepolymers initiated by mono-functional initiators, and the molecular weights of resulting chain-extended products increase several decade times in an hour comparing to the prepolymers. The chain extended products HPPDO-T have better thermal stability, and higher glass transition temperatures and lower crystallization rates than PPDO homopolymer.     

Preparation and characterization of poly(o-methoxyaniline)/Na-MMT clay nanocomposite via emulsion polymerization: Electrochemical studies of corrosion protection

A series of poly(o-methoxyaniline) (PMA)/Na⁺-montmorillonite (MMT) clay nanocomposite (Na⁺-PCN) materials have been successfully prepared by in situ emulsion polymerization in the presence of inorganic nanolayers of hydrophilic Na⁺-MMT clay with DBSA and APS as surfactant and initiator, respectively. The as-synthesized Na⁺-PCN materials were characterized by Fourier-transformation infrared (FTIR) spectroscopy, wide-angle powder X-ray diffraction (XRD) and transmission electron microscopy (TEM).Na⁺-PCN materials in the form of coatings with low loading of Na⁺-MMT clay (e.g., 5 wt.%, CLMA5) on cold rolled steel (CRS) were found much superior in corrosion protection over those of neat PMA based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance spectroscopy in 5 wt.% aqueous NaCl electrolyte. The molecular weight of PMA extracted from Na⁺-PCN materials and net PMA were determined by gel permeation chromatography (GPC) with NMP as eluant. Effects of material composition on the optical properties, electrical conductivity, thermal stability and surface morphology of neat PMA and/or a series of Na⁺-PCN materials, in the form of solution, powder-pressed pellet and fine powder, were also studied by ultraviolet-visible spectra, four-point probe technique, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), respectively.     

The crystal structures of α,ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-aromatic molecule inclusion compounds. IV. (1,6-Diaminohexane)cadmium(II) tetracyanonickelate(II)-m-toluidine(1/1),-p-toluidine(1/1), and-2,4-xylidine(1/1) clathrates,and the coordination complex bis(p-toluidine) (1,6-diaminohexane)cadmium(II) tetracyanonickelate(II)

The crystal structures of the four title compounds have been analyzed by single crystal X-ray diffraction methods at room temperature. Three with a general formula Cd[NH₂(CH₂)₆NH₂]Ni(CN)₄·G (G=m-toluidine,Im;p-toluidine,Ip; and 2,4-xylidine,Ix) are the inclusion compounds of the respective aromatic molecules in the three-dimensional metal complex host (1,6-diaminohexane)cadmium(II) tetracyanonickelate(II). The remaining one is a coordination complex ofp-toluidine, bis(p-toluidine) (1,6-diaminohexane)cadmium(II) tetracyanonick-elate(II),II, Im, Ix, andII crystallize under similar experimental conditions;Ip is obtained using thep-toluidinemesitylene mixture at higher dilution than that used forII. Im crystallizes in the tri linic space group \(P\bar 1\) , witha=9.725(2),b=7.598(1),c=7.177(1) Å, α=90.44(1), β=98.80(1), γ=95.70(1)^o, andZ=1 (the final conventionalR=0.037 for 3526 reflections);Ip: monoclinic,P2/m,a=9.540(2),b=7.611(1),c=7.120(1) Å, β=100.95(1)^o, andZ=1 (R=0.027 for 1700 reflections);Ix: monoclinic,P2/m,a=9.628(2),b=7.613(1),c=7.122(1) Å, β=100.01(1)^o, andZ=1 (R=0.049 for 2704 reflections);II: monoclinic,P2₁/n,a=12.107(3),b=10.117(2),c=12.471(3) Å, β=113.67(2)^o, andZ=2 (R=0.037 for 2616 reflections). The structures ofIm, Ip andIx are similar to that of theo-toluidine inclusion compound of the same metal complex host. InII atrans pair of thep-toluidine molecules to the cadmium atom in the two-dimensional network formed by thecatena-μ-linkages of ?Cd?NH₂(CH₂)₆NH₂?Cd? and ?NC?Ni?CN?Cd?NC?Ni?CN?intersecting at each Cd atom; two cyanide groups of the tetracyanonickelate(II) moiety have free N-ends.     

A new class of aromatic polybenzoxazoles containing ortho-phenylenedioxy groups

A series of poly(o-hydroxy amide)s having both ether and ortho-catenated phenylene unit in the main chain were synthesized via the low-temperature solution polycondensation of 4,4^′-(1,2-phenylenedioxy)dibenzoyl chloride and 4,4^′-(4-tert-butyl-1,2-phenylenedioxy)dibenzoyl chloride with three bis(o-aminophenol)s including 4,4^′-diamino-3,3^′-dihydroxybiphenyl, 3,3^′-diamino-4,4^′-dihydroxybiphenyl, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The poly(o-hydroxy amide)s exhibited inherent viscosities in the range of 0.23-0.96 dl/g. Most of the poly(o-hydroxy amide)s were soluble in polar organic solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) and could afford flexible and tough films by solution casting. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded polybenzoxazoles. However, the polybenzoxazoles were organic-insoluble except for those with the hexafluoroisopropylidene group. The polybenzoxazoles exhibited glass-transition temperatures (T_g) in the range of 200-232 °C by DSC and softening temperatures (T_s) of 250-256 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 500 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 546-606 °C in air and 574-631 °C in nitrogen.     

Poly(N-isopropylacrylamide)/poly[(N-acetylimino)ethylene] thermosensitive block and graft copolymers

Block and graft copolymers with poly(N-isopropylacrylamide) and poly[(N-acetylimino)ethylene] (PNAI) sequences were synthesized via PNAI derivatives (macroinitiators or macromers). The polymerization yields for block copolymers synthesized in ethanol, using the PNAI macroinitiator, were low (<10%), except where photochemical polymerization was applied. By contrast, for the copolymerizations of N-isopropylacrylamide with the PNAI macromers, performed in alcoholic solution, quite high polymerization yields, around 80-90%, were reached. ¹H-NMR and IR spectral and differential scanning calorimeter thermal data confirmed the copolymer formation. Thermosensitivity of the copolymers was investigated by means of turbidimetric technique as a function of their nature, average molecular weight and composition. It was found that the length of the chain of the PNAI macromer and the content in hydrophilic PNAI units of the resulted copolymer affected this behavior.     

Synthesis and characterization of novel vinyl copolymers containing N-vinylphthalimide: Comonomers reactivity ratios and thermal stability

N-Vinylphthalimide (NVPh) was copolymerized with p-methylstyrene (PMS), p-methoxystyrene (PMOS) and p-chlorostyrene (PClS) at 60 °C, with 2,2′-azo-bis-isobutyronitrile as an initiator. Copolymer composition was determined by elemental analysis in case of the N-vinylphthalimide and p-methylstyrene comonomer pair, whereas proton nuclear magnetic resonance was used for the analysis of the two other copolymers.The reactivity ratios for each comonomer pair were estimated by the classical Fineman-Ross and Kelen-Tüdõs linear techniques. These data showed that N-vinylphthalimide was less reactive in all the cases and that the comonomer distribution, that was basically random in the poly(N-vinylphthalimide-co-p-methylstyrene) and poly(N-vinylphthalimide-co-p-chlorostyrene) copolymers, was rather alternate in the third poly(N-vinylphthalimide-co-p-methoxystyrene) copolymer. The difference observed in the reactivity ratios was discussed in reference to the structure of the comonomer units and the parent radicals. The thermal properties of the copolymers and model homopolymers were investigated by differential scanning calorimetry and thermogravimetric analysis.