Synthesis of poly(o‐toluidine) in the presence of magnetic field and dysprosium chloride

The poly‐o‐toluidine (POT) was prepared under different magnetization in solution containing 0.5 mol dm^?3o‐toluidine, 1.0 mol dm^?3 HCl with and without 0.5 mol dm^?3 DyCl₃, respectively. Their conductivity, UV–vis, FTIR spectra, X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscope (SEM) were investigated. The results of conductivity showed that magnetic field and the cooperative effect of Dy³⁺ and magnetic field do obvious effect to conductivity of POT. Meantime, they also can make the energy for the π–π* transitions and quinoid ring transition in UV–vis spectra smaller. At high magnetization the peaks of POT due to Q? NH⁺? B or B? NH⁺? B and C? H out of plane on 1,4‐ring or 1,2,4‐ring disappeared in FTIR spectra. Magnetic field and Dy³⁺ can make three dimensions morphologies of the POT clear, but they scarcely affect the crystallinity of POT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2174–2179, 2007     

Doping effect of organic sulphonic acids on the solid‐state synthesized polyaniline

Polyaniline (PANI) salts doped with organic sulfonic acids (methanesulfonicacid, p‐toluenesulphonic acid, and dodecylbenzenesulphonic acid) were first synthesized by using solid‐state polymerization method. The polymers were characterized by Fourier transform infrared (FTIR) spectra, ultraviolet‐visible spectrometry, X‐ray diffraction, cyclic voltammetry, scanning electron microscopy, transmission electron microscopy, and conductivity measurements. It was found that PANI doped with p‐toluenesulphonic acid is formed in conductive emeraldine oxidation state, and displayed higher doping level and cyrstallinity. On the contrary, PANI doped with dodecylbenzenesulphonic acid was lower at doping level and highly amorphous. In accordance with these results, the conductivity and electrochemical acitivity was also found to be higher in p‐toluenesulphonic acid‐doped PANI, and these properties were opposite in the case of dodecylbenzenesulphonic acid. The results also revealed that the morphology of dodecylbenzenesulphonic acid‐doped PANI was remarkably different from other PANI salts. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Synthesis and characterization of poly(n‐undecyl isocyanate)/polyaniline polyblend

Poly(n‐undecyl isocyanate) (PUDIC)/n‐dodecylbenzenesulfonic acid (DBSA)‐doped polyaniline (PANIDBSA) polyblend was prepared and the effect of the H‐bonding between these two polymers on the compatibility, conjugation chain length of PANIDBSA, and helixity of PUDIC in the polyblend system were studied. The monomer and polymer were characterized by NMR spectra and the polyblend was analyzed by FTIR, UV–vis spectra, and wide‐angle X‐ray diffraction. It was found when the blend composition of the PUDIC was higher than 10%, the WAXD patterns demonstrated lower angle shifting for the peaks at around 2θ = 2–2.5°, referring to the distance between the layers of the layered structure of PANIDBSA crystalline with increasing PUDIC, indicating the expansion of the layered structure of PANIDBSA. The FTIR spectra illustrated the presence of an absorption peak at 1700 cm^?1 shift to higher wave number with PUDIC due to its H‐bonding with PANIDBSA. The UV–vis spectra of PANIDBSA described a blue‐shift of the λ_max with PUDIC, indicating that the presence of PUDIC in the polyblend system can interrupt and decrease the conjugation chain length of PANIDBSA. The optical activity of the helical PUDIC decreased notably with the presence of PANIDBSA, resulting from the reversed helical effect (de‐nature) of H‐bonding. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A water‐soluble supramolecular‐structured photoinitiator between methylated β‐cyclodextrin and 2,2‐dimethoxy‐2‐phenylacetophenone

A water‐soluble supramolecular‐structured photoinitiator (SSPI) was synthesized by supramolecular self‐assembling between methylated β‐cyclodextrin (MβCD) and hydrophobic 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA). The structure of SSPI was characterized by X‐ray diffraction, FTIR, ¹H NMR, UV–vis, and fluorescence spectra. The results indicated that MβCD and DMPA had formed 1 : 1 inclusion complex in methanol solution. The binding constant (K) for the complex was 7.51 × 10²M^?1. SSPI could be dissolved in water easily and its water‐solubility was 15.3 g/100 mL. SSPI was the more efficient photoinitiator than DMPA for the photopolymerization of acrylamide (AM) in homogeneous aqueous system. The conversion for photopolymerization of trimethylolpropane triacrylate system initiated by SSPI was similar to that initiated by DMPA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of poly(N‐methyl aniline) doped with sulphonic acids: Their application as humidity sensors

Single step chemical polymerization of N‐methyl aniline was carried out by using ammonium persulphate as an oxidizing agent. The conducting emeraldine salt phase of the polymers using camphor sulfonic acid and p‐toluene sulfonic acid as dopants was made by a direct process. The polymers were characterized by UV‐vis and FTIR spectroscopy, scanning electron microscopy, TGA, and conductivity measurements. The synthesized polymers were found to have very good physicochemical properties and good electrical conductivity. Conductivity measurements have shown “thermal activated behavior.” The change in resistance with respect to % relative humidity (RH) was observed, when pressed pellets of the polymer were exposed to the broad range of humidity (ranging between 20 and 100% RH). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 812–820, 2006     

Synthesis and properties of polymer from bis‐3,4‐ethylenedioxythiophene substituted acenaphthenequinoxaline

A new electrochoromic polymer poly(8,11‐bis(3,4‐ethylenedioxy thiophen‐2‐yl)acenaphtho[1,2‐b]‐quinoxaline) (PBEAQ) was synthesized by electrochemical polymerization of the corresponding monomer (BEAQ) in a 0.1 M tetraethylammonium tetrafluoroborate (TEABF₄) dichloromethane–acetonitrile (2 : 1, v : v) solution. The monomer and polymer were characterized by elemental analysis, ¹H‐NMR, IR, and UV‐vis spectroscopy. The electrochemical and optical properties of polymer were investigated by cyclic voltammetry and UV‐vis spectroscopy. Cyclic voltammetry and spectroelectrochemistry studies demonstrated that the polymer can be reversibly reduced and oxidized (both n‐ and p‐doped) between ?2 V and +1.5 V vs. Ag/Ag⁺. The polymer had a transmissive light blue color in the oxidized state and reddish color in the reduced state. Undoped polymer shows UV‐vis absorption peaks at 615 nm in solution, 650 nm in solid state, and has an optical band gap of 1.5 eV. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of an oxygen‐ion beam (O+7, 100 MeV) and γ irradiation on polypyrrole films

Nanostructured polypyrrole films doped with para‐toluene sulfonic acid were prepared by an electrochemical process, and a comparative study of the effects of swift heavy ions and γ‐ray irradiation on the structural and optical properties of the polypyrrole was carried out. Oxygen‐ion (energy = 100 MeV, charge state = +7) fluence varied from 1 × 10¹⁰ to 3 × 10¹² ions/cm², and the γ dose varied from 6.8 to 67 Gy. The polymer films were characterized by X‐ray diffraction, ultraviolet–visible spectroscopy, and scanning electron microscopy. The X‐ray diffraction pattern showed that after irradiation, the crystallinity improved with increasing fluence because of an increase in the crystalline regions dispersed in an amorphous phase. The ultraviolet–visible spectra showed a shift in the absorbance edge toward higher wavelengths, which indicated a significant decrease in the band gap of the polypyrrole film after irradiation. The scanning electron microscopy study showed a systematic change in the surface of the polymer. A similar pattern was observed with the γ irradiation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly (N‐methylaniline)/multi‐walled carbon nanotube composites—Synthesis,characterization, and electrical properties

This study described the synthesis of hydrochloric acid (HCl)‐doped poly (N‐methylaniline) (PNMA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Based on the π–π electron interaction between c‐MWNTs and the N‐methylaniline monomer and the hydrogen bond interaction between the carboxyl groups of c‐MWNTs and imine groups of N‐methylaniline monomers, N‐methylaniline molecules were adsorbed on the surface of c‐MWNTs and polymerized to form PNMA/c‐MWNT composites. Scanning electron microscopy images showed that both the thinner fibrous phase and the larger block phase could be observed. The individual fibrous phases had diameters from several tens to hundreds of nanometers, depending on the PNMA content. Transmission electron microscopy proved that PNMA/c‐MWNTs composite fibrous phases were core (c‐MWNT)‐shell (PNMA) tubular structures. The structure of PNMA/c‐MWNT composites was characterized by FTIR, UV–vis spectra, and X‐ray diffraction patterns. The electrical conductivities of PNMA/c‐MWNT composites were much higher than that of PNMA without c‐MWNTs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2356–2361, 2006     

Effects of preparation method on microstructure and properties of UV‐curable nanocomposite coatings containing silica

UV‐curable nanocomposites were prepared by the blending method or the in situ method with nanosilica obtained from a sol–gel process. The microstructure and properties of the nanocomposite coatings were investigated using ²⁹Si‐NMR cross‐polarization/magic‐angle spinning, transmission electron microscopy (TEM), Fourier transform IR (FTIR), differential scanning calorimetry (DSC), and UV–visible (UV–vis) spectra, respectively. The NMR and TEM showed that during the blending method, tetraethyl orthosilicate (TEOS) completely hydrolyzed to form nanosilica particles, which were evenly dispersed in the polymer matrix. However, for the in situ method, TEOS partially hydrolyzed to form some kind of microstructure and morphology of inorganic phases intertwisted with organic molecules. FTIR analysis indicated that the nanocomposites prepared from the in situ method had much higher curing rates than those from the blending method. DSC and UV–vis measurements showed that the blending method caused higher glass‐transition temperatures and UV absorbance than the in situ method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1119–1124, 2005     

Synthesis and characterization of new polyamides containing p‐phenylenediacryloyl moieties in the main chain

Six new polyamides 8a–f containing p‐phenylenediacryloyl moieties in the main chain were prepared by the direct polycondensation reaction of bis(p‐amidobenzoic acid)‐p‐phenylene diacrylic acid 6 with 1,4‐diphenylene diamine 7a , 1,3‐diamino toluene 7b , 1,5‐diamino naphthalene 7c , 4,4′‐diamino diphenyl ether 7d , 4,4′‐diamino diphenyl sulfone 7e , and 3,3′‐diamino diphenylsulfone 7f by using thionyl chloride, N‐methyl‐2‐pyrolidone, and pyridine as condensing agents. These new polymers 8a–f were obtained in high yield and inherent viscosity between 0.35–0.65 dL/g. The resulting polyamides were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility test, FTIR and UV–vis spectroscopy. Diacid acid 6 as a new monomer containing p‐phenylenediacryloyl moiety was synthesized by using a three‐step reaction. First, p‐phenylenediacrylic acid 3 was prepared by reaction of terephthal aldehyde 1 with malonic acid 2 in the presence of pyridine, then diacid 3 was converted to p‐phenylenediacryloyl chloride 4 by reaction with thionyl chloride. Finally, bis(p‐amidobenzoic acid)‐p‐phenylene diacrylic acid 6 was prepared by the condensation reaction of phenylenediacryloyl chloride 4 with p‐aminobenzoic acid 5 . © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chemical synthesis and characterization of some conducting polyaniline derivatives: Investigation of the effect of protonation medium

Poly(o‐toluidine) (POT) and poly(2‐chloroaniline) (P2ClAn) emeraldine salts were synthesized chemically by using formic (HCOOH), acetic (CH₃COOH), propionic (C₂H₅COOH), and boric (H₃BO₃) acids. Ultraviolet‐visible absorption spectra (UV–Vis) analysis results indicated that POT has the better protonation effects than P2ClAn. Among the POTs synthesized using the four different acids, POT(H₃BO₃) showed the least protonation effect. The conductivities of prepared polymers were measured by a four‐probe technique. The highest conductivities were obtained in POTs synthesized by using formic, acetic, and propionic acids. Magnetic susceptibility measurements of the polymer salts were analyzed by using Gouy scale and it was found that POT(CH₃COOH) and POT(C₂H₅COOH) salts are of bipolaron structure; other polymer salts are of polaron structure. The characterization of the polymers were investigated by Fourier infrared spectroscopy (FTIR), UV–Vis, thermogravimetric analysis, and scanning electron microscopy. It was observed from UV–Vis spectra of the emeraldine salt of POT that wavelengths belonging to π → π* transitions shifted to shorter wavelengths with increasing pKa values of acids. POT and P2ClAn synthesized in four different protonation media decomposed with three‐step and three‐ or two‐step weight loss, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1993–2000, 2002; DOI 10.1002/app.10487     

Effect of Co2+, Ni2+, Cu2+, or Zn2+ on properties of polyaniline nanoparticles

Uniform polyaniline (PANI) nanoparticles with typical sizes of about 50 nm were electropolymerized on indium tin oxide surfaces in the presence of Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. According to shaping theory, we first suggest the reason forming PANI spherical particles. Their conductivity, UV‐vis spectra, FTIR spectra, X‐ray diffraction, and thermogravimetric analysis were investigated. The conductivities and crystallinity of PANI doped with these ions are higher than those of PANI doped with HCl (PANI/HCl). Both UV‐vis absorption spectra and FTIR spectra indicate the interactions between Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ and PANI chains. TG analysis also shows that the thermal stability of PANI doped by Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ is lower than that of PANI/HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of novel poly(o‐toluidine) montmorillonite nanocomposites: Effect of surfactant on intercalation

The investigation of clay based polymer nanocomposites has opened the door for the development of novel, ecofriendly advanced nano materials that can be safely recycled. Because of their nanometer size dispersion, these nanocomposites often have superior physical and mechanical properties. In this study, novel nanocomposites of poly(o‐toluidine) (POT) and organically modified montmorillonite (MMT) were synthesized using camphor sulfonic acid (CSA), cetyl pyridinum chloride (CPCl), and N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) to study the role of surfactant modification on the intercalation. The in situ intercalative polymerization of POT within the organically modified MMT layers was analyzed by FTIR, UV–visible, XRD, SEM as well as TEM studies. The average particle size of the nanocomposites was found to be in the range 80–100 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characterization of polydiphenylamine/multi‐walled carbon nanotube composites

We describe the synthesis of methane sulfonic acid (MeSA)‐doped poly(diphenylamine) (PDPA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Diphenylamine monomers were adsorbed on to the surface of c‐MWNTs and polymerized to form PDPA/c‐MWNT composites. SEM and TEM images indicated two different types of materials: the thinner fibrous phase and the larger globular phase. The individual fibrous phase had a diameter around 100–130 nm, which should be the carbon nanotubes (diameter 20–30 nm) coated with a PDPA layer. The structure of PDPA/c‐MWNT composites was characterized by FTIR, UV‐visible spectroscopy and X‐ray diffraction patterns. The electrical conductivities of PDPA/c‐MWNT composites were much higher than that of PDPA without c‐MWNTs. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of a novel oligosiloxane containing alternative ladderlike structure via charge‐transfer interaction

A novel oligosiloxane containing alternative ladderlike structure involving viologen groups has been prepared via donor–acceptor interaction‐assisted template polymerization. The monomer used as the electron‐donor component, N,N ′‐bis(3‐methyldimethoxyl‐silylpropyl)‐4,4′‐bipyridinium dihexafluorophosphate and its precursor, N,N ′‐bis(3‐methyldimethoxyl‐silylpropyl)‐4,4′‐bipyridinium dibromide were first synthesized successfully in high yield. This oligosiloxane, which displays interesting electrochromic properties, has been characterized by FTIR, UV–vis, ¹H NMR, ²⁹Si NMR, X‐ray diffraction (XRD), and vapour pressure osmometry (VPO). © 2001 Society of Chemical Industry     

Synthesis and characterization of electrically conducting copolymer of aniline and o‐bromoaniline using methane sulfonic acid as dopant

Polyaniline (PAN), poly(o‐bromoaniline) (POBA), and poly(aniline‐co‐o‐bromoaniline) (PABA) were synthesized by oxidative coupling. These polymers are protonated by 10–20% methane sulfonic acid (MSA) and 1M HCl. The new polymer bases have greater solubility than that of PAN in common polar organic solvents; PAN–MSA was observed to be the most thermally stable of these polymers. POBA is associated with residual quinoid diimine units as illustrated in the IR and UV‐vis spectra, after reduction with hydrazine dihydrochloride. Both the doping agents cause a downward shift of the quinoid absorption in the IR spectra. MSA‐ and HCl‐doped PAN and PABA polymers exhibit a coil‐like conformation in DMSO, whereas only MSA‐doped PAN and PABA show an “expanded coil‐like” conformation in m‐cresol with a “free carrier tail” above 800 nm in their electronic spectra. XPS spectra indicated the presence of covalent bromine in the POBA and PABA polymers. Bromine retention was greater in the homopolymer as evidenced by the IR studies after aging at 350°C. Compared to HCl, MSA is found to be a more effective dopant, enhancing the conductivity of the copolymers by 10²–10³ times in magnitude. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2662–2669, 2002     

A simple one‐step chemical route to gold/polymer core/shell composites and polymer hollow spheres

Au/poly(o‐toluidine) (POT) core/shell composite spheres have been successfully fabricated by chemical polymerization route in aqueous solution without the aid of surfactant or functional acids using HAuCl₄ as the oxidant. By altering the concentration of oxidant, the amount of Au nanoparticles inside each POT sphere can be tuned from tens to one. Moreover, uniform POT hollow spheres with one opening in each polymer surface can be obtained under extremely low concentration of oxidant. The chemical structures of Au/POT composites were confirmed by Fourier transform infrared (FTIR), UV‐vis, and X‐ray diffraction (XRD) spectroscopies. Moreover, the formation mechanisms of Au/POT core/shell composites and POT hollow spheres were also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

UV‐Triggered Optical Response and Oxygen Scavenging Ability of a Water‐Soluble Poly(N,N‐dimethylacrylamide‐co‐2‐vinylbenzylanthraquinone) Copolymer

A vinyl‐modified anthraquinone (AQ) derivative (Vinyl‐AQ) is synthesized through a palladium‐mediated Suzuki coupling reaction between vinylphenylboronic acid and 2‐chloromethylanthraquinone and, subsequently, copolymerized with N,N‐dimethylacrylamide (DMAM) through free radical copolymerization in organic solvent. The chemical structure of the resulting water‐soluble copolymer, P(DMAM‐co‐AQ), is verified using techniques such as proton nuclear magnetic resonance, attenuated total reflection‐infrared spectroscopy, thermogravimetric analysis, and UV–vis spectroscopy. The evolution of the oxygen scavenging abilities of aqueous P(DMAM‐co‐AQ) solutions after UV irradiation is monitored as a function of UV irradiation time, concentration of AQ moieties, and pH. The copolymer is proved an effective UV‐triggered oxygen scavenger, leading to dissolved oxygen contents below 1 ppm for the optimized experimental conditions. This behavior is related with the appearance of novel chemical species with interesting optical properties, as suggested by the respective evolution of the UV–vis absorption and photoluminescence spectra after UV irradiation.     

Synthesis and characterization of a ferrocene‐modified,polyaniline‐like conducting polymer

A novel monomer called 1,1′‐ferrocenediacyl anilide (FcA) was synthesized from ferrocene (Fc). Copolymerization was carried out between FcA and aniline (ANI) by an electrochemical method. The novel monomer and copolymer were characterized with ¹H‐NMR, Fourier transform infrared (FTIR) spectroscopy, and ultraviolet–visible (UV–vis) spectroscopy. The hydrogen protons of the benzene ring were moved to a low field in ¹H‐NMR, and the absorption band of N?Q?N (where Q is the quinoid ring) appeared in the FTIR spectrum of the polymer. The peaks of both Fc and the π–π* electronic transition in the UV–vis spectra were redshifted. The results indicate that the copolymer mainly existed as a highly delocalized conjugated system. X‐ray diffraction analysis established further proof, and the process of electrochemical deposition was observed by scanning electron microscopy. The optimal synthesis conditions of the copolymer were determined through changes in the monomer molar ratios and the scan rate. The ideal performance of the copolymer was gained when the monomer molar ratio between FcA and ANI was 1:4 and the scan rate was 50 mV/s. Furthermore, the electrochemical performances were tested in detail by cyclic voltammetry, galvanostatic charge–discharge testing, and electrochemical impedance spectroscopy. The results show that the specific capacitance of poly(1,1′‐ferrocenediacyl anilide‐co‐aniline) increased up to 433.1 F/g at 0.5 A/g, the diffusion resistance was very small, and the durability was good enough. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43217.