Synthesis and characterization of tanninsulfonic acid doped polyaniline–metal oxide nanocomposites

Composites of conducting polymers and metal oxides have a potential role in electronic devices because of their enhanced physical and electronic properties. An in situ synthesis of metal oxide nanocomposites of polyaniline (PANI) and tanninsulfonic acid doped PANI was carried out at ?10°C with two different ratios of aniline to sodium persulfate (oxidant) and the simultaneous incorporation of TiO₂, Al₂O₃, and ZnO nanopowders. The products were characterized by X‐ray diffraction (XRD), thermal analysis, spectroscopy, and electrical conductivity measurements. XRD and thermogravimetric analysis confirmed the presence of the metal oxide in the final product, whereas the spectroscopic characterization revealed interactions among the tannin, metal oxides, and PANI. The electrical properties were determined by four‐point‐probe bulk conductivity measurements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of novel two‐component conjugated polythiophenes with 3‐octyl and 3‐isooctylthiophene side chains

With copolymerization functionalization, a novel solution‐processable polymer, poly{(3‐octylthiophene)‐co‐[3‐(2‐ethyl‐1‐hexyl)thiophene]} (P3OTIOT), combining the electrochemical properties of poly(3‐octylthiophene) (P3OT) and poly[3‐(2‐ethyl‐1‐hexyl)thiophene] (P3IOT) was synthesized by the FeCl₃‐oxidative approach. The characterization of the polymers included Fourier transform infrared, ¹H‐NMR, gel permeation chromatography, thermogravimetric analysis (TGA), ultraviolet–visible spectroscopy, and photoluminescence (PL). P3OTIOT had excellent solubility in common organic solvents. Investigations of the optical properties showed that the optical band‐gap energy of P3OTIOT was similar to that of P3OT (2.43 eV) at 2.45 eV and 6% lower than that of P3IOT in CHCl₃ solutions. The bandwidth of the P3OTIOT absorption approached that of P3OT, ranging from 370 to 570 nm, and the emission maximum of P3OTIOT was only 50 nm blueshifted with respect to that of P3OT. However, the PL intensity of P3OTIOT was 7 times higher than that of P3OT. TGA studies showed that P3OTIOT had very good thermal stability, losing 5% of its weight on heating to 300°C. It is suggested that P3OTIOT has low band‐gap energy, a high PL quantum yield, and processability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1169–1175, 2007     

Synthesis and photovoltaic properties of dithienyl benzotriazole based poly(phenylene vinylene)s

Two new alternating copolymers based on dithienyl benzotriazole segment and phenylene vinyl unit were synthesized by Heck cross coupling method. The polymers exhibited broad absorption bands (from 300 nm to 752 nm for P1 , and from 300 nm to 654 nm for P2 ) in the UV‐visible region with optical bandgap ranging between 1.6 and 1.9 eV and proper electronic energy levels measured by cyclic voltammetry. The photovoltaic properties of the polymers as electron donors with 6.6‐phenyl C61‐butyric acid methyl ester as the electron acceptor in a bulk heterojunction structures were reported. Preliminary results showed moderate power conversion efficiency of 0.36% and 0.4%, respectively, under the illumination of AM 1.5, 100 mW/cm² with a device structure of ITO/PEDOT : PSS/polymer : PC₆₀BM (1 : 3)/Ca/Al. Furthermore, the side chain effect on properties has also been investigated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of carboxymethyl chitosan containing functional ultraviolet absorber substituent

A series of carboxymethyl chitosan (CMC) with 2.4‐dihydoxybenzophenone (UV‐0) substituent were synthesized by the Mannich reaction of CMC hydrochloride and UV‐0 in the solvent of methanol and water. The different molar degree of substitution (MS) was achieved by changing the UV‐0 content. The effects of MS on ultraviolet absorbability, crystallinity, moisture‐absorption and ‐retention property, and photostability were investigated respectively. The obtained products were characterized by means of Fourier transform infrared spectra (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR), X‐ray diffraction, and UV spectrophotometer. It was found that the grafted products were water‐soluble, and the increased MS values could enhance the moisture‐retention property and photostability, while decreased the crystallinity and moisture‐absorption property. The ultraviolet absorption peaks became stronger by introducing UV‐0 into the CMC backbones. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Electrical resistivity and magnetoresistivity of protonic acid (h2SO4 and HCl)‐doped polyaniline at low temperature

Electrical‐transport properties of protonic acid (H₂SO₄ and HCl)‐doped polyaniline (PANI) in an aqueous ethanol medium were investigated in the temperature range 1.8 K ≤ T ≤ 300 K and in a magnetic field up to 8 T. The room‐temperature resistivity of HCl‐doped PANI is larger than that of H₂SO₄‐doped PANI. The resistivity ratios ρ_r = ρ(1.8 K)/ρ(300 K) of the samples are high. The samples in the insulating region show a crossover from a Mott to an Efros–Shklovskii variable range hopping conduction at T = 9.8 K for H₂SO₄‐doped PANI and 8.5 K for HCl‐doped PANI. The magnetoresistivity of these samples is also explained by the variable range hopping theory. The different physical parameters were calculated from the experimental data. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1480–1486, 2000     

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,characterization, and photochemical properties of chromophores containing photoresponsive azobenzene and stilbene

In this article, we describe the synthesis of two azobenzene and two stilbene‐based diacetylene chromophores containing terminal electron‐donating (? OCH₃) and electron‐withdrawing (? NO₂) terminal groups with esterification reactions. The target compounds were characterized by NMR, X‐ray diffraction (XRD), absorption, and photoluminescence spectroscopies. We investigated the structural effects of these photochromic compounds on the E–Z photoisomerization and 1,4‐addition under UV irradiation. 4‐[(4‐Nitrophenyl)‐diazenyl]phenyl pentacosa‐10,12‐diynoate, incorporating the electron‐withdrawing nitro group (? NO₂), underwent the fastest rate of Z‐to‐E isomerization in darkness via a rotation mechanism. Our results demonstrate that self‐assembled azobenzene Z isomers exhibited enhanced fluorescence under UV irradiation. XRD spectroscopy identified bilayer packing by the polydiacetylene films after 1,4‐addition. Chromophores comprising the diacetylene group presented moderate photochromic stability upon 1,4‐addition, changing from their original yellowish color to form a blue phase. These synthesized compounds may be useful in the development of new and unique functional materials that exhibit bistable photochromism. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of 4,4′-diacryloyloxybenzophenone

A copolymerizable type II photoinitiator 4,4′-diacryloyloxybenzophenone (DABP) based on 4,4′-dihydroxybenzophenone (DHBP) and acryloyl chloride was synthesized, and its structure was confirmed by ¹H NMR and real-time infrared spectroscopy. UV–vis absorption spectroscopy of DABP exhibited red-shifted maximal absorption as compared with benzophenone (BP). The kinetics of photopolymerization was studied by real-time infrared spectroscopy. It showed that DABP was a more effective photoinitiator than benzophenone. When this photointiator and amine was used to efficiently initiate polymerization of acrylates and methacrylates, both rate of polymerization and final conversion increased and the induction period was shortened with increase of amine concentration, DABP concentration and light intensity.     

Synthesis of nitropyridine‐based π‐conjugated polymers and their chemical properties

π‐Conjugated poly(3‐nitropyridine‐2,5‐diyl) ( PPy‐3‐NO₂ ), poly(3,3′‐dinitro‐2,2′‐bipyridine‐5,5′‐diyl) ( PBpy‐3,3′‐diNO₂ ), and a poly(arylene ethynylene) type polymer consisting of a 3,3′‐dinitro‐2,2′‐bipyridine unit ( PAE‐1 ) were synthesized by Cu‐promoted Ullmann coupling reaction and Pd‐catalyzed coupling reaction. PPy‐3‐NO₂ and PAE‐1 were soluble in organic solvents such as DMSO, DMF, and chloroform, and gel permeation chromatography analysis showed a number average molecular weight (M_n) of 9,300 and 12,300, respectively. PPy‐3‐NO₂ gave intrinsic viscosity, [η], of 0.53 dL g^?1 in DMF. PBpy‐3,3′‐diNO₂ had somewhat lower solubility. The polymers exhibited a UV–vis peak at about 430 nm. PPy‐NO₂ received electrochemical reduction at ?1.5 V versus Ag⁺/Ag in acetonitrile, and gave an electrochemical redox cycle in a range from 0 to ?1.1 V versus Ag⁺/Ag in an aqueous solution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1763–1767, 2006     

POMA/PMMA blends modified by dye: Spectroscopic and morphological properties

Poly(o‐methoxyaniline) (POMA), a conductive polymer (CP) well known, was used to prepare blends with poly(methyl methacrylate) (PMMA). Conducting polymer keeps absorbance strength within the PMMA matrix. POMA/PMMA blends presented absorption bands regarding the conducting polymer with different intensities and the main band red shifting. However, POMA/PMMA blends showed no photoluminescence (PL) emission. After the hybridization process of the CP with a photoluminescent dye, 2,1,3‐benzothiadiazole, POMA/PMMA blends showed new optical properties. PL spectra revealed an emission in the range of 500–550 nm, indicating interaction between the dye and the conducting polymer. The presence of the dye modified the morphological properties of the POMA/PMMA blends. New features have appeared on the surface of the blends prepared with higher concentration of hybridized CP. Blends with lower concentrations of hybridized CP showed their surfaces with POMA globules being covered by PMMA. This morphology replaced the globules and “crystals” on the surface of the blends prepared without the dye. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of soluble polyaniline

Polyaniline, which is soluble in common organic solvents, has been synthesized through the oxidative chemical polymerization of aniline in the presence of benzene diazonium chloride salt in an aqueous HCl acid medium. The blue‐black polyaniline thus prepared exists in a lower oxidation state than emeraldine. An X‐ray photoelectron spectroscopy study has shown that the intrinsic oxidation state of the polymer is 0.38. An elemental analysis has shown that the fractional doping level or degree of oxidation of the blue‐black polyaniline is 0.26. The product is believed to consist of a lower number of imine nitrogens in comparison with the polyemeraldine base. This fact is also corroborated by the lower electrical conductivity of the polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Facile synthesis of hollow microspheres of polyaniline using poly(sodium 4‐styrenesulfonate) as dopant

In a conventional chemical oxidative polymerization of aniline in poly(sodium 4‐styrenesulfonate) aqueous solution, hollow microspheres of polyaniline were easily prepared, instead of common particles. The morphology of the hollow microspheres was studied and confirmed using scanning electron microscopy and transmission electron microscopy. The molecular structure, room temperature conductivities and thermal stability of the resulting polyaniline were characterized using Fourier transform infrared spectroscopy, the standard DC four‐probe method, thermogravimetric analysis and differential thermal analysis. The influence of poly(sodium 4‐styrenesulfonate) and aniline on the morphology and physical properties of the resulting polymer were investigated. The results showed that the proper ratio of poly(sodium 4‐styrenesulfonate) and aniline was a critical factor in the synthesis of hollow microspheres, which may be related to the chemical structure of poly(sodium 4‐styrenesulfonate) as polyanion and of polyaniline as polycation and the electrostatic interaction between them in the doping process. A possible formation mechanism is proposed in this work. © 2013 Society of Chemical Industry     

Synthesis and structural characterization of a new polysiloxane with second‐order nonlinear optical effect

A new polysiloxane ( P2 ), with a high density of the indole‐based chromophore and carbazolyl side groups, was prepared. Thus a polysiloxane ( P1 ), with indole and carbazolyl groups as side chains, was first synthesized through a hydrosilylation reaction, and then the post‐azo coupling of p‐nitrobenzenediazonium fluoroborate toward the indole ring gave the mulifunctional indole‐based chromophore‐functionalized polysiloxane ( P2 ). Molecular structural characterization for the polymers was determined by ¹H‐NMR, IR, and UV–visible spectra, gel permeation chromatography, and differential scanning calorimetry. The polymers were easily soluble in common organic solvents. The poled film of P2 revealed a resonant d₃₃ value of 27 pm/V by second‐harmonic generation measurements. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 769–774, 2004     

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     

Preparation and characterization of PS‐PMMA/ZnO nanocomposite films with novel properties of high transparency and UV‐shielding capacity

High transparent and UV‐shielding poly (styrene)‐co‐poly(methyl methacrylate) (PS‐PMMA)/zinc oxide (ZnO) optical nanocomposite films were prepared by solution mixing using methyl ethyl ketone (MEK) as a cosolvent. The films were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) spectra, high‐resolution transmission electron microscopy (HR‐TEM), and atomic force microscope (AFM). Cross‐section HR‐TEM and AFM images showed that the ZnO nanoparticles were uniformly dispersed in the polymer matrix at the nanoscale level. The XRD and FTIR studies indicate that there is no chemical bond or interaction between PS‐PMMA and ZnO nanoparticles in the nanocomposite films. The UV–vis spectra in the wavelength range of 200–800 nm showed that nanocomposite films with ZnO particle contents from 1 to 20 wt % had strong absorption in UV spectrum region and the same transparency as pure PMMA‐PS film in the visible region. The optical properties of polymer are greatly improved by the incorporation of ZnO nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and photopolymerization characterization of a novel difunctional photoinitiator

A novel difunctional photoinitiator HBP‐TDI‐HBP based on 4‐hydroxybenzophenone (HBP) and toluene‐2,4‐diisocyanate (TDI) was synthesized and characterized by ¹H NMR and UV–Vis absorption spectroscopy. The kinetics of photopolymerization was studied by real‐time infrared spectroscopy. It showed that HBP‐TDI‐HBP was a more effective photoinitiator than benzophenone. When this photointiator and amine were used to efficiently initiate polymerization of acrylates and methacrylates, both rate of polymerization and final conversion increased with increase of HBP‐TDI‐HBP concentration, light intensity, and amine concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New antimicrobial agents: The synthesis of Schiff base polymers containing transition metals and their characterization and applications

A new polymeric Schiff base containing formaldehyde and 2‐thiobarbituric acid moieties was synthesized by the condensation of a monomeric Schiff base derived from 2‐hydroxyacetophenone and hydrazine. Polymer–metal complexes were also synthesized by the reaction of the polymeric Schiff base with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) acetate. The polymeric Schiff base and its polymer–metal complexes were characterized with magnetic moment measurements, elemental analyses, and spectral techniques (infrared, ¹H‐NMR, and ultraviolet–visible). The thermal behaviors of these coordination polymers were studied by thermogravimetric analysis in a nitrogen atmosphere up to 800°C. The thermal data revealed that all of the polymer–metal complexes showed higher thermal stabilities than the polymeric Schiff base and also ascribed that the Cu(II) polymer–metal complex showed better heat resistant properties than the other polymer–metal complexes. The antimicrobial activity was screened with the agar well diffusion method against various selected microorganisms, and all of the polymer–metal complexes showed good antimicrobial activity. Among all of the complexes, the antimicrobial activity of the Cu(II) polymer–metal complex showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of water‐soluble conducting polyaniline by enzyme catalysis

Enzymatic synthesis of a water‐soluble, conducting polyaniline (PANI) was studied, using horseradish peroxidase as the biocatalyst and H₂O₂ as the initiator, in the presence of a poly(vinylsulfonic acid, sodium salt) (PVS) polyanion template. The effects of the buffer, concentration of H₂O₂, and the molar ratio of aniline to PVS on the polymerization were particularly investigated. The products were characterized by UV–vis/near‐IR and FTIR spectroscopy, thermogravimetric analysis, and four‐point probe conductivity measurement. The results showed that PVS could be chosen as a new template in the synthesis of PANI. The proper conditions of polymerization were obtained as follows: pH of the buffer was pH 4.0–5.0, the concentration of H₂O₂ was around 20 mM, and the molar ratio of PVS to aniline was 1–1.5. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 814–817, 2005     

Optical and structural properties of polyvinyl alcohol loaded with different concentrations of lignosulfonate

Polyvinyl alcohol/lignosulfonate (PVA/LS) composite films have been prepared using casting technique. The effect of lignosulfonate concentrations (0.001, 0.005, 0.01, 0.05, 0.1 and 0.5 wt %) on the optical and structural properties of polyvinyl alcohol (PVA) has been investigated using UV–vis spectroscopy and X‐ray diffraction. The results indicate that, the addition of LS led to a more compact structure of PVA, which resulted in an increase in its refractive index and amorphous phase. This was associated with a reduction in the optical energy gap that could be attributed to the increase in disorder structural of the composites. Moreover, the transmittance of PVA/LS composite film decreased with the increase of LS doping concentrations onto the PVA matrix. The results reflect the proper dispersion of LS in the PVA matrix that causes a strong intermolecular interaction between LS and PVA suggesting strong hydrogen bond formation between the hydroxyl group in PVA chains and the outer site groups of LS. Further, the transmission of the samples in the wavelength range of 370–780 nm, as well as any color changes, was studied. The color intensity ΔE, which is the color difference between the pure PVA sample and those with different LS concentration, increases with increasing the LS content and was accompanied by an increase in the yellow and red color components. J. VINYL ADDIT. TECHNOL., 25:85–90, 2019. © 2018 Society of Plastics Engineers     

Synthesis,characterization, and thermal aging behavior of HCl‐doped polyaniline/TRGO nanocomposites

In this article polyaniline (PANI) nanocomposites containing thermally reduced graphene oxide (TRGO) were synthesized and characterized before and after thermal aging. The nanocomposites were prepared through in situ oxidative polymerization of aniline in the presence of TRGO nanoplatelets. FTIR and Raman spectroscopies, XRD, FESEM, and electrical conductivity measurements were used to characterize synthesized materials. PANI/TRGO nanocomposites showed considerably higher electrical conductivity when compared to pure PANI, which was associated with the higher electrical conductivity of TRGO and increased crystallinity of PANI in the presence of TRGO. Pure PANI and PANI/TRGO nanocomposites were thermally aged at 70, 80, 90, and 100 °C. The results showed that the characteristic time of thermal aging process is higher for PANI/TRGO nanocomposites and increases with TRGO loading, which indicates better stability of conductivity during thermal aging process. On the other hand, the characteristic time of thermal aging reduced with aging temperature and a fast decrease was observed from 80 to 90 °C. Improved resistance over thermal aging can be attributed to the barrier effect of TRGO nanoplatelets to the dopant molecules, which retards conductivity degradation in the thermal aging process. Furthermore, TRGO increases PANI crystallinity and it can also prevent crystallinity reduction during thermal aging process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44635.