Blend of electroactive poly(3-dodecylthiophene) with comb-like alkylated polyacrylate

The conformational mode change of the stiff alkylated polymer, poly(3-dodecyl thiophene) (PDDT), with a flexible comb-like coil poly(octadecyl acrylate) (PODA), and the effect of intermolecular interaction between these two alkylated polymers with different chemical structure of the backbone were investigated using UV-Vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimeter (DSC), and wide-angle x-ray diffraction (WAXD). In addition to the characteristics of thermochromism, a homogeneous one phase was observed above 175°C when the PODA content was 10 wt % or less. Increased conductivity in the PDDT/PODA blend due to the highly conjugated π-system of PDDT backbone was observed in the presence of nonelectroactive PODA. A red-shift of absorption maximum of PDDT/PODA blend observed in solid state at room temperature. From the FTIR spectra, the gauche-trans conformational structure change of methylene units was investigated in two alkylated polymer blends. The increase of combined heat of fusion of the alkyl side chain melting of PDDT and the endothermic peak of PODA, as well as the interlayer d-spacing of PDDT main chain were also observed with the addition of PODA in blends. A more ordered conformational structure of rigid rod backbone of PDDT was induced due to the attractive intermolecular interaction which can cause cocrystallization between the alkylated side chains of two polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 :1025–1041, 1997     

Electrically conductive,melt‐processed ternary blends of polyaniline/dodecylbenzene sulfonic acid,ethylene/vinyl acetate,and low‐density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004     

Conductivity and structure of melt‐processed polyaniline binary and ternary blends

In the present study, conductive binary and ternary blends containing polyaniline (PANI) were developed through melt blending. The binary blends' investigation focused on the morphology, in light of the components' interaction, and the resulting electrical conductivity. Similar solubility parameters of a given doped PANI and a matrix polymer lead to dispersion of fine PANI particles within the matrix, and to formation of conducting paths at low PANI contents. A plasticizer acting also as a compatibilizer improves the matrix polymer/PANI interactions. In ternary blends consisting of PANI and two immiscible polymers, the PANI preferrentially locates in one of the components, affecting the blend's morphology. This “concentrating” effect leads to relatively high electrical conductivity at a low PANI content. The electrical conductivity of the studied ternary blends is almost independent of the components' sequence of addition into the hot melt mixing device, exhibiting the selectivity of PANI towards one of the components. Copyright © 2000 John Wiley & Sons, Ltd.     

Miscibility enhancement and formation of interpenetrating spherulites in ternary blends of crystalline polymers

Miscible blends of three crystalline polymers, namely poly(butylene succinate) (PBS), poly(ethylene succinate) (PES), and poly(oxyethylene) (POE), exhibited interpenetrating spherulites, where a spherulite of one component grows inside the spherulites of other components. PBS and PES were immiscible above the melting points, T_m, of these substances, while ternary blends with POE showed miscibility, which depended on the molecular weight of POE. PBS and PES exhibited the same spherulitic growth process as in a miscible binary blend when they were crystallized from a homogeneous ternary melt. Spherulites of PBS, which is the highest‐T_m component, filled the whole volume first when a miscible ternary blend was quenched below T_m of POE, the lowest‐T_m component. Then, the blends showed either two types of crystallization processes. One was successive nucleation and growth of PES and POE spherulites, that is, PES nucleated and developed spherulites inside the PBS spherulites and then POE spherulites grew inside the interlocked spherulites of PBS and PES. The other was simultaneous growth and the formation of interpenetrating spherulites of PES and POE inside the PBS spherulites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 706–711, 2010     

Poly(silmethylene)-based polymer blends. I. In situ polymerization of 1,3-disilacyclobutanes in silicon-based polymers

The in situ polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane with or without a catalyst in flexible organo-silicon polymers was demonstrated to provide poly(silmethylene)-based polymer blends. An alternative route, which implies preparation of blends via synthesis of a flexible polymer in the presence of a rigid polymer, was also promising. The resulting polymer blends were characterized by DSC, dynamic mechanical analysis, and solvent extraction. No chemical interaction is observed between component polymers of blends prepared by the in situ bulk polymerization method while formation of block or graft copolymers comprising poly(diphenylsilmethylene) and flexible polymers is suggested when in situ copper-catalyzed polymerization was employed. A morphological difference between samples synthesized by the different methods was suggested by microscopic observation. © 1997 John Wiley & Sons, Inc.     

Stable aqueous dispersion of reduced graphene nanosheets via non-covalent functionalization with conducting polymers and application in transparent electrodes

We developed a simple and facile method of producing a stable aqueous suspension of reduced graphene oxide (RGO) nanosheets through the chemical reduction of graphene oxide in the presence of a conducting polymer dispersant, poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). This approach involves the cooperative interactions of strong π- π interactions between a two-dimensional graphene sheet and a rigid backbone of PEDOT and the intermolecular electrostatic repulsions between negatively charged PSS bound on the RGO sheets, which impart the colloidal stability of the resulting hybrid nanocomposite of RGO/PEDOT. Moreover, our one-step solution-based method allows preserving the intrinsic chemical and electronic properties of both components, yielding a hybrid film of RGO nanosheets of high conductivity of 2.3 kΩ/sq with a transmittance of 80%. By taking advantage of conducting network structure of conducting polymers which provides an additional flexibility and mechanical stability of RGO nanosheets, we demonstrate the potential application of hybrid RGO/PEDOT as highly flexible and transparent electrodes.     

On the structure and electrical conductivity of polyaniline/polystyrene blends prepared by an aqueous‐dispersion blending method

This article describes electrically conductive polymer blends containing polyaniline‐dodecyl benzene sulfonic acid (PANI‐DBSA) dispersed in a polystyrene (PS) matrix or in crosslinked polystyrene (XPS). Melt blending of previously mixed, coagulated, and dried aqueous dispersions of PANI‐DBSA and PS latices lead to high conductivities at extremely low PANI‐DBSA concentrations (∼0.5 wt % PANI‐DBSA). In these blends, the very small size of the PANI‐DBSA particles and the surface properties (with surfactants used) of both the PANI and polymer particles play a major role in the PANI‐DBSA particle structuring process. The PANI‐DBSA behavior is characteristic of a unique colloidal polymeric filler with an extremely high surface area and a strong interaction with the matrix, evidenced by a significantly higher glass‐transition temperature of the matrix. The effect of the shear level on the conductivity and morphology of the PS/PANI‐DBSA blends was studied by the production of capillary rheometer filaments at various shear rates. An outstanding result was found for XPS/PANI‐DBSA blends prepared by the blending of aqueous XPS and PANI‐DBSA dispersions. Some of these blends were insulating at low shear levels; however, above a certain shear level, smooth surface filaments were generated, with dramatically increased and stable conductivities. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 611–621, 2001     

Impedance study of thiolated polyaniline

Covalent attachment of thiolated probes to conducting polymers such as polyaniline (PANI) is a promising approach towards the development of electrochemical sensors and biosensors. However, thiolation alters the conjugated polymer backbone and influences the electrochemical behavior of the conducting polymer. PANI studied in this work was electropolymerized on glassy carbon (GC) electrodes from a solution of 0.1 M aniline in 0.5 or 1.0 M H₂SO₄. The GC/PANI electrodes were then functionalized by covalent attachment of 2-mercaptoethanol to the PANI backbone. The progress of thiolation was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Thiolation of PANI was found to cause an initial decrease in electroactivity at 0–0.25 V and an increase in electroactivity at 0.25–0.6 V. However, prolonged thiolation caused a loss of electroactivity of PANI, which could be seen from EIS measurements as a dramatic decrease in the bulk redox capacitance of PANI.     

Conductive poly(butadiene-co-acrylonitrile)-polyaniline dodecylbenzenesulfonate [NBR-PAni.DBSA] blends prepared in solution

Blends of poly(butadiene-co-acrylonitrile) elastomer [NBR] and polyaniline dodecylbenzenesulfonate [PAni.DBSA], with electrical conductivities up to 10⁻² S cm⁻¹, have been prepared by solution mixing and casting. Miscibility was maximised for NBR with high acrylonitrile (ACN) content, as predicted on the basis of simple solubility parameter calculations. Blends prepared using NBR with 48 wt% ACN had the lowest electrical conductivity percolation thresholds, and were much more conductive than previous thermally mixed blends. Optical and electron micrographs of blends prepared from NBR 48 wt% ACN also showed the lowest levels of phase separation. The FT-IR spectra of NBR-PAni.DBSA blends resembled a superposition of the spectra of the pure materials, but with significant peak shifts due to changing intermolecular interactions between the polymers. Under DSC analysis, thermal events for blends prepared with NBR 48 wt% ACN also showed the largest temperature shifts relative to those for the pure polymers, supporting the other evidence for interaction between the two polymers.     

Synthesis of poly(1.4.-benzamide) in solutions of randomly coiled polymers

The polycondensation of p-aminobenzoic acid by the use of triphenylphospine and hexachloroethane is described. One way to obtain a mixed solution of rigid rod and flexible coil polymers is the polycondensation of the rigid chains in a solution of a flexible polymer matrix. Results on matrix polycondensation of poly(p-benzamide) in solutions of poly(methyl methacrylate), poly(methyl methacrylate-co-styrene), polystyrene and polyacrylonitrile are reported. It is shown that there exists an interrelation between the phase behavior of the mixed polymer solutions and the influence of the matrix polymer on the synthesis of poly(1.4.-benzamide). The ternary phase diagrams of the rigid rod/flexible coil polymer solutions were determined.     

Effect of preparation method on nanoscopic structure of conductive SBS/PANI blends: Study using small‐angle X‐ray scattering

Small‐angle X‐ray scattering (SAXS) studies of electrically conductive blends based on polyaniline–dodecylbenzenesulfonic acid (PANI–DBSA)/styrene–butadiene–styrene (SBS) triblock copolymer were performed to investigate the influence of the blend preparation procedure on the nanoscopic structure of the blends. The blends were prepared by mechanical mixing (MM) procedure and by in situ polymerization (ISP) of aniline in the presence of SBS. The results indicate that pure PANI–DBSA presents an extended phase consisting of crystalline islands of nanometric size, with a good spatial correlation between them, embedded into an amorphous PANI phase. This feature was not observed in SBS/PANI–DBSA blends prepared by MM or ISP. In MM blends, the PANI phase is constituted by smaller domains, containing poorly spatially correlated crystalline islands, whereas in ISP blends with low or medium amount of PANI, there is no SAXS peak which could be related to a spatial correlation between PANI crystalline islands. The conductivity of the ISP blends is higher when compared to MM blends because of the higher homogeneity at nanometric scale. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3069–3077, 2007     

The conformation of poly(3-dodecyl thiophene) within methacrylic polymer matrix

Blends of poly(3-dodecyl thiophene) (PDDT) with poly(methyl methacrylate), poly(butyl methacrylate) (PBMA), and poly(methyl methacrylate-co-butyl methacrylate) (PMMA/PBMA) were studied by polarization optical microscopy, atomic-force microscopy, and absorption spectroscopy and were modeled using molecular dynamics (MD) simulations. The observed thermochromic transitions are shown to be host-matrix dependent, with PDDT/PBMA absorption spectra differing substantially from pristine PDDT. The dispersion of PDDT within PBMA matrix is observed to be greater than in the other host polymers. MD calculations of both individual PDDT molecules and molecular aggregates suggest that the distribution of dihedral angles present in the PDDT backbone is the narrowest for aggregates of PDDT embedded within a polymer matrix. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2909–2917, 1999     

Miscibility studies of poly(3-octylthiophene)/poly(ethylene-co-vinylacetate) blends with a solvatochromatic shift in the solid state

The mixing of electrically conducting polymers in the undoped state with flexible polymers has been limited due to the stiffness of the delocalized coplanar backbone. The substitution with alkyl side chains has resulted in the distortion of the aromatic rings in the backbone with an increase of the flexibility. The alkyl substituents also prevent the thiophene back-bones from packing together, thus making blending with other polymers promising. We have investigated the phase behavior of poly(3-octylthiophene) (P3OT) with a flexible polymer, poly(ethylene-co-vinylacetate) (vinylacetate composition 20%, EVA20), and defined a miscibility window based on melting point data, on cloud point measurements, and on analysis by optical microscopy. The miscible region has been studied by UV-VIS and CPMAS NMR spectroscopies. A UV absorption in the visible region originates from a π-π ^* transition in the delocalized structure of P3OT, and a change in the length of the conjugated segment in the backbone results in a shift of this absorption. A gradual solvatochromatic shift of P3OT in the solid state with dilution was observed in the miscible region. T₁ relaxation times for the methylene carbons in solid state show a gradual change in the relaxation process as a function of composition. © 1995 John Wiley & Sons, Inc.     

Significance of miscibility in multidonor bulk heterojunction solar cells

Ternary organic blends have potential in realizing efficient bulk heterojunction (BHJ) organic solar cells by harvesting a larger portion of the solar spectrum than binary blends. Several challenging requirements, based on the electronic structure of the components of the ternary blend and their nanoscale morphology, need to be met in order to achieve high power conversion efficiency in ternary BHJs. The properties of a model ternary system comprising two donor polymers, poly(3-hexylthiophene) (P3HT) and a furan-containing, diketopyrrolopyrrole-thiophene low-bandgap polymer (PDPP2FT), with a fullerene acceptor, PC₆₁BM, were examined. The relative miscibility of PC₆₁BM with P3HT and PDPP2FT was examined using diffusion with dynamic secondary ion mass spectrometry (dynamic SIMS) measurements. Grazing incidence small and wide angle X-ray scattering analysis (GISAXS and GIWAXS) were used to study the morphology of the ternary blends. These measurements, along with optoelectronic characterization of ternary blend solar cells, indicate that the miscibility of the fullerene acceptor and donor polymers is a critical factor in the performance in a ternary cell. A guideline that the miscibility of the fullerene in the two polymers should be matched is proposed and further substantiated by examination of known well-performing ternary blends. The ternary blending of semiconducting components can improve the power conversion efficiency of bulk heterojunction organic photovoltaics. The blending of P3HT and PDPP2FT with PC₆₁BM leads to good absorptive coverage of the incident solar spectrum and cascading transport energy levels. The performance of this ternary blend reveals the impact of the miscibility of PC₆₁BM in each polymer as a function of composition, highlighting an important factor for optimization of ternary BHJs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 237–246     

Oxygenation of conducting polymers facilitated by structure-breaking anions

Conducting polymers are an interesting class of materials that can be tuned to have a range of properties through counterion doping. For most conducting polymers, the insertion of anions (the doping process) leads to the formation of carbocations (positive charge carriers) along the conjugated polymer backbone. In this research, we report on a scenario that arises where certain (commonly used) anions in water induce oxygenation of the conducting polymers heteroatom. This is in contrast to the widely reported doping process, and the recently reported hydrolysis of conducting polymers. We observe that the transition between these different conducting polymer-interactions/reactions is well described by the concept of structure-making and structure-breaking anions. Poly(3,4-propylenedioxy thiophene dimethyl) (PProDOT-Me₂), polypyrrole (PPy), and poly(3,4-ethylenedioxy thiophene) (PEDOT) thin films are exposed to a range of anions in water. Both PProDOT-Me₂ and PPy are susceptible to oxygenation, while in contrast PEDOT is doped, when exposed to structure-breaking anions. All the polymers show hydrolysis for structure-making anions. The knowledge of the interaction and/or reaction of conducting polymers with anions in water is not only critical to their application in devices for aqueous environments (i.e., sensing), but also for their processing and fabrication using water.     

Compositional dependence of the open-circuit voltage in ternary blend bulk heterojunction solar cells based on two donor polymers

Ternary blend bulk heterojunction (BHJ) solar cells containing as donor polymers two P3HT analogues, high-band-gap poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) (P3HT(75)-co-EHT(25)) and low-band-gap poly(3-hexylthiophene-thiophene-diketopyrrolopyrrole) (P3HTT-DPP-10%), with phenyl-C(61)-butyric acid methyl ester (PC(61)BM) as an acceptor were studied. When the ratio of the three components was varied, the open-circuit voltage (V(oc)) increased as the amount of P3HT(75)-co-EHT(25) increased. The dependence of V(oc) on the polymer composition for the ternary blend regime was linear when the overall polymer:fullerene ratio was optimized for each polymer:polymer ratio. Also, the short-circuit current densities (J(sc)) for the ternary blends were bettter than those of the binary blends because of complementary polymer absorption, as verified using external quantum efficiency measurements. High fill factors (FF) (>0.59) were achieved in all cases and are attributed to high charge-carrier mobilities in the ternary blends. As a result of the intermediate V(oc), increased J(sc) and high FF, the ternary blend BHJ solar cells showed power conversion efficiencies of up to 5.51%, exceeding those of the corresponding binary blends (3.16 and 5.07%). Importantly, this work shows that upon optimization of the overall polymer:fullerene ratio at each polymer:polymer ratio, high FF, regular variations in V(oc), and enhanced J(sc) are possible throughout the ternary blend composition regime. This adds to the growing evidence that the use of ternary blends is a general and effective strategy for producing efficient organic photovoltaics manufactured in a single active-layer processing step.     

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.     

Effect of aniline formaldehyde resin on the conjugation length and structure of doped polyaniline: Spectral studies

A DBSA (n‐dodecylbenzene sulfate)‐complexed aniline formaldehyde [AF(DBSA)_1.0] was successfully synthesized with excess aniline (compared with formaldehyde) in the presence of n‐dodecylbenzene sulfonic acid (HDBSA), which was complexed with aniline monomer before polymerization. The resin was carefully characterized with ¹H and ¹³C NMR, electron spectroscopy for chemical analysis, and Fourier transform infrared and was demonstrated to be a polymer in which anilines were all complexed with HDBSA and became anilinium salts. A drastic decrease of the maximum absorption wavelength (ultraviolet–visible spectra) of DBSA‐doped polyaniline [PANI(DBSA)_0.5] was found when AF(DBSA)_1.0 was mixed, and this resulted from the reduced conjugation length. A similar effect on PANI(DBSA)_0.5 was found when free HDBSAs were mixed with PANI(DBSA)_0.5. Visual inspection with an optical microscope revealed that PANI(DBSA)_0.5/AF(DBSA)_1.0 gave uniform morphologies in various compositions, showing possible miscibility for this system. X‐ray diffraction patterns of PANI(DBSA)_0.5/AF(DBSA)_1.0 showed that the layered structure of PANI(DBSA)_0.5 was still present but became shorter in the polyblend because of the presence of AF(DBSA)_1.0. Solid‐state ¹³C NMR spectra revealed that the reduced conjugation length was derived from the interaction of alkyl groups between HDBSA, complexed DBSA, and dopant DBSAs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3116–3125, 2005     

Complete miscibility of ternary aryl polyesters demonstrating a new criterion and horizon for miscibility characterization

A ternary miscible blend system comprising only crystallizable aryl polyesters [poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(butylene terephthalate)] was characterized with the criteria of thermal analyses, microscopy, and X‐ray characterizations. The reported ternary miscibility (in the quenched amorphous state of blends of the three aryl polyesters) was truly physical and under the condition of no chemical transesterifications; this justified that transesterification was not a necessary condition for miscibility in polyester blends in this case. This study further proposed and tested a novel concept of a new criterion for miscibility characterization for polymer blends of only crystallizable polymers. A single composition‐dependent cold‐crystallization‐temperature (T_cc) peak in blends of only semicrystalline polymers was taken as an indication of an intimate mixing state of miscibility. The theoretical background for establishing the single composition‐dependent T_cc peak as a valid miscibility criterion for crystallizable polymer blends was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2394–2404, 2003     

Self-assembled networks of conducting polyaniline in bulk polymers: A new class of conducting polymer blends

This review of the current status of conducting polymers will focus on recent progress which demonstrates that the initial promise of the late 1970's has become reality. Conducting polymers are now available as materials with truly unique properties: They combine the important electronic and optical properties of semiconductors and metals with the attractive mechanical properties and processing advantages of polymers. Conducting polymer blends based upon polyaniline (PANI) are a new class of materials in which the threshold for the onset of electrical conductivity (σ) can be reduced to volume fractions below 1%, well below that required for classical percolation (16% by volume for globular conducting objects dispersed in an insulating matrix in three dimensions). The origin of this remarkably low threshold for the onset of electrical conductivity is the self-assembled network morphology of the PANI polyblends which forms during the course of liquid-liquid separation. Since the average density of the conducting network near threshold is small, the conductivity increases smoothly and continuously over many orders of magnitude as the concentration of conducting polymer increases above threshold. The low percolation threshold and the continuous increase of σ(f) above threshold are particularly important; as a result of this combination, conducting polyblends can be reproducibly fabricated with controlled levels of electrical conductivity while retaining the desired mechanical properties of the matrix polymer.^1-3)