Synthesis and Characterization of Polyindole/Poly(vinyl acetate) Conducting Composites

Composites of a polyindole (PIN) and poly(vinyl acetate) (PVAc) were prepared chemically using FeCl₃ as an oxidant agent in anhydrous media. The composite compositions were altered by varying the indole monomer during preparation. The composites were characterized by FTIR and UV‐visible spectroscopies, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), stress‐strain experiments and conductivity measurements. Moreover, the film of PVAc and PIN/PVAc composites were prepared by casting on glass Petri dishes to examine their stress‐strain properties. PIN/PVAc composites are thermally more stable than PIN. It was found that the conductivities of PIN/PVAc composites depend on the indole content in the composites.     

Effect of synthetic route on structural and morphological properties of poly(thiophene-co-indole)

In this study, homopolymers of polythiophene (PT), polyindole (PIN) and their composites and copolymers were synthesized by chemical polymerization and were characterized by FTIR and UV-spectroscopy, and conductivity measurements. The conductivities of polymers, composites and copolymers were measured by a conventional four probe method at room temperature and different temperatures. Among the products, PT-PIN copolymer which was synthesized at polythiophene conditions revealed the highest conductivity with a value of 0.28 S cm^?1. The thermal properties of the samples were investigated by using thermogravimetric analyses, and it was found that they have quite good thermal stability. X-ray diffraction spectra showed that the amorphous nature of the polymers. Morphological properties of the polymers, composites and copolymers have been investigated by scanning electron microscopy.     

Conductive triethylene glycol monomethyl ether substituted polythiophenes with high stability in the doped state

Synthesis of two conducting polymers containing 3‐hexylthiophene and 3‐[2‐(2‐(2‐methoxyethoxy)ethoxy)ethoxy]thiophene is demonstrated. In thin‐film transistors, the high‐molecular‐weight polymer shows an average mobility of 4.2 × 10^?4 cm² V^?1 s^?1. Most importantly, the polymers have high conductivity upon doping with iodine and also have high stability in the doped state with high conductivities measured even after 1 month. Furthermore, the doping causes transparency to thin films of the polymer and the films are resistant to common organic solvents. All these properties indicate a great potential for the iodine‐doped polymer to be used as an alternative to commercially available poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1079–1086     

Multifunctional poly(2,5‐benzimidazole)/carbon nanotube composite films

The AB‐monomer, 3,4‐diaminobenzoic acid dihydrochloride, was recrystallized from an aqueous hydrochloric acid solution and used to synthesize high‐molecular‐weight poly(2,5‐benzimidazole) (ABPBI). ABPBI/carbon nanotube (CNT) composites were prepared via in situ polymerization of the AB‐monomer in the presence of single‐walled carbon nanotube (SWCNT) or multiwalled carbon nanotube (MWCNT) in a mildly acidic polyphosphoric acid. The ABPBI/SWCNT and ABPBI/MWCNT composites displayed good solubility in methanesulfonic acid and thus, uniform films could be cast. The morphology of these composite films was studied by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The results showed that both types of CNTs were uniformly dispersed into the ABPBI matrix. Tensile properties of the composite films were significantly improved when compared with ABPBI, and their toughness (～200 MPa) was close to the nature's toughest spider silk (～215 MPa). The electrical conductivities of ABPBI/SWCNT and ABPBI/MWCNT composite films were 9.10 × 10^?5 and 2.53 × 10^?1 S/cm, respectively, whereas that of ABPBI film was 4.81 × 10^?6 S/cm. These values are ～19 and 52,700 times enhanced by the presence of SWCNT and MWCNT, respectively. Finally, without acid impregnation, the ABPBI film was nonconducting while the SWCNT‐ and MWCNT‐based composites were proton conducting with maximum conductivities of 0.018 and 0.017 S/cm, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1067–1078, 2010     

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.     

Design and synthesis of optically transparent calcium‐incorporated polymer complexes

Transparent thin films of calcium‐ion‐incorporated polymer composites were synthesized with calcium carbonate (CaCO₃) and polymers such as poly(acrylic acid) (PAA), poly(ethylene glycol) (PEG), and methylcellulose. The homogeneous distribution of Ca²⁺ in the composite films was observed because of the high concentration of COO^? groups along the PAA backbone for the complexation of Ca²⁺ ions. The optical transparency of the composites depends on the weight percentages of the three polymers and the molar concentration of CaCO₃ in the composites. Maximum transparency was obtained for a composite film with a PAA/CaCO₃ ratio of 9:1. The results indicated that methylcellulose improved the film‐forming capabilities and that PEG improved the transparency of the composites. All polymer complexes were characterized with X‐ray diffraction, fourier transfer infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, dynamic mechanical analysis, and optical transparency measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4459–4465, 2004     

Electrokinetic and electrorheological properties of poly(vinyl chloride)/polyindole conducting composites

In this study, poly(vinyl chloride) (PVC), polyindole (PIN), and PVC/PIN conducting composites having five different compositions were used. Particle sizes, densities, dielectric constants, and sedimentation ratios of the materials were determined. The zeta‐potentials of the samples were measured in aqueous and nonaqueous (silicone oil [SO]) media. The dispersions prepared in SO were subjected to external electric field strength, and their electrorheological properties were investigated. Then the effects of dispersed particle volume fraction, shear rate, external electric field strength, frequency, and temperature onto electrorheological activities of the dispersions were examined. Further, creep and creep‐recovery tests were applied to the PIN/SO and PVC/PIN/SO dispersions, and reversible viscoelastic deformations were observed. Finally, the vibration damping capacity of PVC (66%)/PIN (34%)/SO dispersion system was tested by using an automobile shock absorber. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,Characterization and Electrorheological Properties of Polyindene/Kaolinite Composites

In this study, synthesis, characterization and electrorheological (ER) properties of polyindene (PIN) and polyindene/kaolinite composites were carried out by cationic radical polymerization using FeCl₃ as the oxidizing agent. The homopolymer and composites, containing different amounts of PIN were characterized by FTIR spectroscopy, thermo‐gravimetric (TGA) analyses, scanning electron microscopy (SEM) and dynamic light scattering (DLS) methods. The conductivity and dielectric properties of PIN and PIN/kaolinite composites were determined. Suspensions of PIN and PIN/kaolinite composites were prepared in silicone oil (SO), at a series of concentrations (c=5–25 m/m %). The effects of concentration, shear rate, electric field strength, frequency, temperature and promoter on ER activities of suspensions were investigated.     

Low‐potential facile electrosynthesis of free‐standing poly(1H‐benzo[g]indole) film as a yellow‐light‐emitter

High‐quality free‐standing poly(1H‐benzo[g]indole) (PBIn) films were synthesized electrochemically by direct anodic oxidation of 1H‐benzo[g]indole (BIn) in boron trifluoride diethyl etherate. PBIn films obtained from this medium showed good electrochemical behavior and better thermal stability with a conductivity of 0.29 S cm^?1. PBIn films with low band gap value (1.59 eV) were insoluble in acetone and tetrahydrofuran. The structure and morphology of the polymer were studied by UV–vis, FTIR, and scanning electron microscopy, respectively. The results of quantum chemistry calculations and the spectroscopies of dedoped PBIn indicate that the polymerization of BIn mainly occurs via C₍₂₎ and C₍₅₎ position. The polymer film was compact with regular nanoparticles on the surface. Fluorescent spectral studies indicate that solid‐state PBIn film is a good yellow‐light‐emitter. Thermal stability of PBIn film is higher than poly(indole‐6‐carboxylic acid), poly(5‐formylindole), and polyindole. To the best of our knowledge, this is the first report on the electrosynthesis of free‐standing polyindole derivatives as yellow‐light‐emitter. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2730–2738     

Regioregular poly[3‐(4‐alkoxyphenyl)thiophene]s

An easy synthetic procedure for soluble poly[3‐(4‐alcoxyphenyl)thiophene]s is reported. The polymers present a high regioregularity degree as determined by both UV–vis spectra and ¹H and ¹³C NMR analysis. Furthermore, X‐ray powder diffraction analysis performed on films of the polymers suggests a π‐stacked packing structure of the macromolecules. Electrical characterization was performed on one of the synthesized polythiophenes on both undoped and doped (with FeCl₃ or iodine) films. The conductivity and charge‐carrier mobility were assessed by current–voltage and field effect measurements. Well‐structured polymer films were obtained simply via spin coating from chloroform solutions and without the need of further processing, unlike other regioregular polythiophenes reported in the literature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1758–1770, 2007     

Poly(terthiophene)s from copolymer precursors via solid‐state oxidative conversion

Herein, we report the synthesis of conducting poly (terthiophene)s using a side chain precursor polymer approach. Random copolymers were prepared by ring opening metathesis polymerization of two norbornylene monomers, one containing a pendant terthiophene group and the other containing a pendant acetate group. Solid‐state oxidative conversion of the terthiophene units was used to produce conductive polymers. Oxidative solid‐state conversion was successful for copolymers containing as little as 1 mol % of terthiophene comonomer. The electrical and optical properties of CPs were studied as a function of the amount of electroactive moiety, terthiophene (3T), present in the copolymer. The CPs were found to have conductivity varying between 10^?1 and 10^?4 S/cm depending on the precursor copolymer compositions. The CPs obtained from all precursors had no significant difference in their energy gaps and showed blue to orange color transitions when switching from the oxidized to the neutral states, respectively. The absorbance intensity at 426 nm for poly(3T) from the precursors fits the Beer–Lambert law corresponding to the range of initial 3T content in the precursor copolymer composition (from 1 to 100 mol %). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 756–763, 2010     

Electrosyntheses of freestanding polyindole films in boron trifluoride diethyl etherate

High‐quality freestanding polyindole (PIn) films were synthesized electrochemically through the direct oxidation of indole in pure boron trifluoride diethyl etherate (BFEE). The oxidation potential of indole in this medium was measured to be only 0.86 V versus a saturated calomel electrode, which was lower than that determined in acetonitrile/0.1 mol L^?1 Bu₄NBF₄. PIn films obtained from this medium showed better electrochemical behavior and better thermal stability with a conductivity of 10^?1 S cm^?1, and this indicated that BFEE was a better medium than acetonitrile for the electrosyntheses of PIn films. Structural studies showed that the polymerization of indole ring occurred at the 2,3‐position. As‐formed PIn films could be partly dissolved in acetone, acetonitrile, tetrahydrofuran, and so forth. Fluorescent spectral studies indicated that PIn was a good blue‐light emitter. To the best of our knowledge, this is the first report on the fluorescence of PIn. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1444–1453, 2005     

Facile electrochemical preparation of poly(9,9‐dichlorofluorene), a new polyfluorene derivative as green light emitter

High‐quality poly(9,9‐dichlorofluorene) (PDCF), a new part soluble polyfluorene derivative, was easily synthesized electrochemically by direct anodic oxidation of 9,9‐dichlorofluorene (DCF) in boron trifluoride diethyl etherate (BFEE) containing 15% (by volume) trifluoroacetic acid (TFA). It was hard for DCF to deposit on the electrode in neutral solvents such as CH₃CN system. This methodology may help promotion of researches to reveal unknown properties and applications of polyfluorene materials. PDCF films with conductivity of 3.3 × 10^?2 S cm^?1 obtained from this media show good redox activity and thermal stability. The structure and morphology of the polymer were studied by UV–vis, FTIR, ¹H NMR spectra, and scanning electron microscopy, respectively. The results of quantum chemistry calculations and the spectroscopies of dedoped PDCF indicate that the polymerization of DCF mainly occurs via C₍₂₎ and C₍₇₎ position. Fluorescent spectral studies indicate that PDCF film with high fluorescence quantum yields and photochemical stability is a novel green light emitter. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1791–1799, 2010     

Proton transportation in an organic–inorganic hybrid polymer electrolyte based on a polysiloxane/poly(allylamine) network

A new class of proton‐conducting polymer was developed via the sol–gel process from amino‐containing organic–inorganic hybrids by the treatment of poly(allylamine) with 3‐glycidoxypropyltrimethoxysilane doped with ortho‐phosphoric acid. The polymer matrix contains many hydrophilic sites and consists of a double‐crosslinked framework of polysiloxane and amine/epoxide. Differential scanning calorimetry results suggest that hydrogen bonding or electrostatic forces are present between H₃PO₄ and the amine nitrogen, resulting in an increase in the glass‐transition temperature of the poly(allylamine) chain with an increasing P/N ratio. The ³¹P magic‐angle spinning NMR spectra indicate that three types of phosphate species are involved in the proton conduction, and the motional freedom of H₃PO₄ is increased with increasing P/N ratios. The conductivity above 80 °C does not drop off but increases instead. Under a dry atmosphere, a high conductivity of 10^?3 S/cm at temperatures up to 130 °C has been achieved. The maximum activation energy obtained at P/N = 0.5 suggests that a transition of proton‐conducting behavior exits between Grotthus‐ and vehicle‐type mechanisms. The dependence of conductivity on relative humidity (RH) above 50% is smaller for H₃PO₄‐doped membranes compared with H₃PO₄‐free ones. These hybrid polymers have characteristics of low water content (23 wt %) and high conductivity (10^?2 S/cm at 95% RH), making them promising candidates as electrolytes for fuel cells. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3359–3367, 2005     

Proton‐conducting electrolytes based on silylated and sulfonated polyetheretherketone: Synthesis and characterization

A derivative of polyetheretherketone (PEEK) having sulfonic acid groups and silicon‐containing substituents covalently bound to the aromatic backbone has been prepared as proton‐exchange membrane material. The polymer 4 (PhSiSPEEK) has been synthesized via (i) sulfonation of PEEK up to 0.9 degree of sulfonation (DS, the number of sulfonic groups per repeat unit), (ii) conversion of sulfonated PEEK 1 (SPEEK09) into sulfonyl chlorinated derivative 2 (PEEKSO₂Cl), (iii) lithiation of 2 and subsequent addition of PhSiCl₃, followed by hydrolysis. The chemical structure of the synthesized polymers has been investigated by ¹H NMR and ¹³C NMR and ATR/FTIR spectroscopy and their thermal stability has been evaluated by thermogravimetric analysis. The presence of inorganic moieties increases the thermal stability of 4 with respect to the sulfonated and not silylated product. Despite its very high DS, PhSiSPEEK is insoluble in water but does not possess the plastic properties needed to be used as an electrolyte membrane. Blend membranes made of SPEEK05 (DS = 0.5) and containing 10 and 25 wt % of 4 (DS = 0.9, degree of silylation DSi = 0.1) have been prepared and characterized by water uptake measurements and electrochemical impedance spectroscopy. The combination of the two functionalized polymers having different properties allows to obtain proton‐conducting electrolytes that are potential candidates for fuel cells applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2178–2186, 2010     

Lightweight electromagnetic shields using optimized polyaniline composites in the microwave band

A genetic algorithm (GA) was used to optimize a multilayer electromagnetic shield of polyaniline (PANI)–polyurethane (PU) conducting composites in the microwave band. First, the electronic properties of freestanding films with different mass fractions of polyaniline were studied. A very low percolation threshold (0.2%) was found, with a maximum of conductivity of 10⁴ S/m. Second, the electromagnetic shielding effectiveness of the films were investigated in the X and Ku bands (8.2–18 GHz), showing an attenuation increase of 1–40 dB with the mass fraction of polyaniline in the blends. Then, the electromagnetic shielding properties of multi‐layered PAni–PU composites were investigated in order to obtain an attenuation superior to 40 or 80 dB, depending on the application. To improve the performances of the electromagnetic shields, three‐layered PAni–PU composites were made, using an optimization method. The intrinsic physical parameters of the composites were used as a database for the optimization calculation. The optimization results showed that materials with a thickness of <500 µm could answer many industrial or military shielding applications. As the electronic properties can be tuned easily with the mass fraction of polyaniline in the blends, conducting multi‐layered composite materials can be made following the results of the optimization. Their electromagnetic shielding effectiveness was measured, showing good agreement between the measurements and modeling. These results demonstrated that the genetic algorithm allows us to conceive lightweight and high performance electromagnetic shields using intrinsically conducting polymers. The mass per unit of surface of the shield was <200 g/m², giving potential applications in the aeronautics domain. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and evaluation of photoluminescent and electrochemical properties of new aromatic polyamides and polyimides with a kink 1,2‐phenylenediamine moiety

A series of novel triphenylamine‐containing aromatic polyamides and polyimides having a crank and twisted noncoplanar structures were synthesized in inherent viscosities of 0.14–0.64 dL/g and 0.11–0.67 dL/g, respectively. These polymers had useful levels of thermal stability associated with relatively high glass‐transition temperatures (174–311 °C). They exhibited strong UV–Vis absorption bands at around 300 nm in NMP solutions. The PL spectra of these polymers in NMP solutions (1 × 10^?5 M) showed maximum peaks around 396–479 nm. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammetry (CV) of the polymer films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at potentials of 0.70–1.01 V and 1.10–1.46 V, respectively, vs. Ag/AgCl in acetonitrile solution. The polymer films revealed electrochromic characteristics, with a color change from neutral pale yellowish to green and then to a blue oxidized form at applied potentials ranging from 0.00 to 1.75 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2587–2603, 2006     

Preparation and characterization of PVC/PANI conductive composite with extremely low percolation threshold

Aniline was polymerized in the presence of poly(vinyl chloride) (PVC) powders in hydrochloric acid to in situ prepare poly(vinyl chloride)/polyaniline (PVC/PANI) composite particles. UV‐vis spectra and FT‐IR spectra indicate PANI in PVC/PANI composite particles possessed a higher oxidation state with decreased aniline content in reactants. Both conductivity and impact strength of the dodecylbenzenesulfonic acid (DBSA) doped PANI composites (PVC/PANI‐DBSA), which were compression molded from the in situ prepared PVC/PANI particles, increase with the pressing temperature and decrease with the increase of DBSA doped PANI (PANI‐DBSA) loading. An excellent electric conductivity of 5.06 × 10^?2 S/cm and impact strength of 0.518 KJ/m² could be achieved for the in situ synthesized and subsequently compression molded composite. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis of metal (Fe or Pd)/alloy (Fe–Pd)‐nanoparticles‐embedded multiwall carbon nanotube/sulfonated polyaniline composites by γ irradiation

Composites of multiwall carbon nanotubes (MWCNTs) and sulfonated polyaniline (SPAN) were prepared through the oxidative polymerization of a mixture of aniline, 2,5‐diaminobenzene sulfonic acid, and MWCNTs. Fe, Pd, or Fe–Pd alloy nanoparticles were embedded into the MWCNT–SPAN matrix by the reduction of Fe, Pd, or a mixture of Fe and Pd ions with γ radiation. Sulfonic acid groups and the emeraldine form of backbone units in SPAN served as the source for the reduction of the metal ions in the presence of γ radiation. The existence of metallic/alloy particles in the MWCNT–SPAN matrix was further ascertained through characterization by high‐resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, thermogravimetric analysis, and conductivity measurements. HRTEM pictures clearly revealed the existence of Fe, Pd, and Fe–Pd nanoparticles of various sizes in the MWCNT–SPAN matrices. There were changes in the electronic properties of the MWCNT–SPAN–M composites due to the interaction between the metal nanoparticles and MWCNT–SPAN. Metal‐nanoparticle‐loaded MWCNT–SPAN composites (MWCNT–SPAN–M; M = Fe, Pd, or Fe–Pd alloy) showed better thermal stability than the pristine polymers. The conductivity of the MWCNT–SPAN–M composites was approximately 1.5 S cm^?1, which was much higher than that of SPAN (2.46 × 10^?4 S cm^?1). Metal/alloy‐nanoparticle‐embedded, MWCNT‐based composite materials are expected to find applications in molecular electronics and other fields. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3355–3364, 2006     

Synthesis of networked polymers with lithium counter cations from a difunctional epoxide containing poly(ethylene glycol) and an epoxide monomer carrying a lithium sulfonate salt moiety

Poly(ethylene glycol)‐based networked polymers that had lithium sulfonate salt structures on the network were prepared by heating a mixture of poly(ethylene glycol) diglycidyl ether (PEGGE), poly(ethylene glycol) bis(3‐aminopropyl) terminated (PEGBA), and an ionic epoxy monomer, lithium 3‐glycidyloxypropanesulfonate (LiGPS). Flexible self‐standing networked polymer films showed high thermal stability, low crystallinity, low glass transition temperature, and good mechanical strength. The materials were ion conductive at room temperature even under a dry condition, although the ionic conductivity was rather low (10^?6 to 10^?5 S/m). The ionic conductivity increased with the increase in temperature to above 1 × 10^?4 S/m at 90 °C. The film samples became swollen by immersing in propylene carbonate (PC) or PC solution of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The samples swollen in PC showed higher ionic conductivity (ca.1 × 10^?3 S/m at room temperature), and the samples swollen in LiTFSI/PC showed much higher ionic conductivity (nearly 1 S/m at room temperature). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3113–3118, 2010