Synthesis of a soluble conjugated copolymer based on dialkyl-substituted dithienothiophene and its application in photovoltaic cells

A soluble conjugated alternating 3,5-didecanyldithieno[3,2-b:2′,3′-d]thiophene-thiophene copolymer was synthesized by palladium(0)-catalyzed Stille coupling reaction. The thermal, absorption, emission, electrochemical, and photovoltaic properties of the polymer were examined. A weight-average molecular weight around 6.2 × 10⁴ and a polydispersity index of 1.8 was estimated for the polymer using gel permeation chromatography. The polymer exhibits good thermal stability with decomposition temperature of 340 °C and glass-transition temperature of 136 °C. The polymer shows strong absorption peaked at 505 nm in diluted solution and 518 nm in thin film with an optical band gap 2.0 eV. The polymer exhibits intense emission located at 550 nm in solution and 603 nm in film. The HOMO and LUMO energies of the polymer were estimated to be −5.4 and −3.4 eV, respectively, by cyclic voltammetry. Polymer solar cells were fabricated based on the blend of the polymer and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM). The power conversion efficiency of 0.7% was achieved under AM 1.5, 100 mW/cm² using polymer:PCBM (1:4, w/w) as active layer.     

Synthesis of sequential poly(1,3-phenyleneethynylene)-based polyradicals and through-space antiferromagnetic interaction of their solid state

Some 1,3-PPE-based polyradicals with pendent phenoxy radicals whose repeating unit consisted of four 1,3-phenyleneethynylene units were synthesized via polymerization between monomers and trimeric monomers in the presence of the Pd(PPh₃)₄ complex catalysts. The ESR spectra of the polyradicals in dichloromethane showed unimodal broad signals. For the solid samples which were prepared from the dichloromethane solution by evaporating the solvent and by drying in vacuo, the signal intensity decreased with broadening of peak-to-peak line-width (ΔH_pp). However, the ESR spectra almost recover to the initial intensity and shapes due to redissolving in dichloromethane. In particular, the decrease of doubly integrating the ESR signal (I_ESR) was more remarkable for the polyradical bearing galvinoxyl and phenoxyl residues than others. This behavior suggests that strong antiferromagnetic interaction partially arose for the polyradical.     

An electrochromic diquat-quaterthiophene alternating copolymer: A polythiophene with a viologen-like moiety in the main chain

A bis-bithiophenyl derivative of diquat, 3,10-bis(2,2′-bithiophene-5-yl)-6,7-dihydropyrido[1,2-a:2′,1′-c]pyrazinodiynium hexafluorophosphate (bt2dq), was synthesized by quaternization of 5,5″-bis(2,2′-bithiophene-5-yl)-2,2′-bipyridine with 1,2-dibromoethane. Its UV–vis absorption spectrum is explained by TD-DFT calculations. It shows the electrochemical properties characteristic for bipyridinium salts (viologens and diquats) and can be electropolymerized to form a conjugated polymer composed of alternating quaterthiophene and diquat blocks. The polymer has been characterised by cyclic voltammetry and UV–vis spectroelectrochemistry: it can be reversibly oxidized, with spectral signs of p-doping of the oligothiophene blocks, and reversibly reduced, with formation of viologen-like cation radicals, which dimerize or form π-stacks.     

Electrochemical analysis of the adsorption and desorption behaviors of carboxylic acid and anhydride monomers onto zinc surfaces

The interfacial bondings formed between succinic acid and myristic acid, as well as succinic anhydride molecules with a set of differently treated zinc substrates have been investigated using infrared reflection absorption spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The compounds were selected to model typically used carboxylic-based adhesives and coatings. Moreover, the adsorption kinetic has been evaluated by means of chronoamperometry (CA) and chronovoltammetry measurements. XPS results showed a relation between the amount of carboxylates formed by adsorption of succinic acid/myristic acid and the hydroxyl fraction presented on the surfaces as proved by a higher electron transfer in CA. On the other hand a set of oxidative/reductive interactions was detected during the adsorption of succinic anhydride, in turn proving a spontaneous ring opening and adsorption mechanism. A clear relationship between the amount of adsorbents and surface hydroxyls/carbonates was detected for the adsorption of succinic anhydride. The extent to which the formed carboxylates resisted negative potentials was also investigated by cyclic voltammetry (CV) in an aqueous solution. The coordinative bonding of a bifunctional carboxylic acid group to the oxide surface was found to be not stable in the presence of a negative potential, while a monofunctional carboxylic acid group could resist displacement by water for a prolonged period of time. On the other hand, a low double layer capacitance was obtained after the adsorption of succinic anhydride, which was related to a change in potential of zero charge (PZC) upon the adsorption.     

Synthesis and properties of carbazole-based hyperbranched conjugated polymers

Carbazole-based novel hyperbranched conjugated polymers linked with triphenylamine and benzene moieties were synthesized by Sonogashira coupling polycondensation of N-octadecyl- and N-octyl-3,6-diethynylcarbazoles with tris(4-iodophenyl)amine and 1,3,5-tribromobenzene. Solvent-soluble polymers with number-average molecular weights in the range of 3500-21,000 were obtained in 48-66% yields. The UV-vis absorption bands of the polymers were red-shifted compared to that of carbazole, indicating the extension of conjugation length. The polymers emitted blue-green fluorescence with high quantum yields up to 67% in CHCl₃. Poly(1/3) containing triphenylamine units emits visible light and shows unique solvatochromism. The polymers were electrochemically redox-active.     

Synthesis and Characterization of Polyacetylene with Side-chain Thiophene Functionality

A new polyacetylene derivative with electroactive thiophene substituent, namely poly(2-methylbut-2-enyl thiophene-3-carboxylate) was synthesized and characterized. For this purpose, novel acetylene monomer was synthesized by the reaction of 3-thiophenecarboxylic acid with propargyl bromide and polymerized with a Rh catalyst to give the corresponding polymer. The chemical structure of the polymer was characterized to comprise the conjugated backbone and electroactive thiophene side group. UV spectral changes of the polymer with temperature were also studied. The polymer exhibited better thermal stability than the unsubstituted polyacetylenes.     

Synthesis and characterization of fluorene-carbazole and fluorene-phenothiazine copolymers with carbazole and oxadiazole pendants for organic light emitting diodes

We report the synthesis and characterization of new series of the fluorene based polymers with carbazole and oxadiazole pendants for the generation of the white emission out of the EL device. In the fluorene backbone, hole transporting units such as carbazole or phenothiazine were incorporated to improve the EL brightness and efficiency. The PFCzOxd-co-PCzs and PFCzOxd-co-PPTZs in EL spectra showed maximum peaks at around 430 nm and additional large peaks at around 530 and 500 nm, respectively. In case of PFCzOxd-alt-PCz and PFCzCzPCz-co-PFOxdOxdPCz, the EL spectra of the polymers showed two distinct peaks comprising the maximum at 427 nm, which corresponds to the EL spectra of the conjugated backbone, and additional broad peaks at around 540 and 530 nm, respectively. The CIE coordinates of the devices from PFCzOxd-alt-PCz and PFCzCzPCz-co-PFOxdOxdPCz were (0.28, 0.33) and (0.25, 0.32), respectively, approaching the value of the standard white of National Television System Committee (NTSC) (0.33, 0.33).     

Creep and recovery behaviors of a polythiophene-based electrorheological fluid

We investigate the creep response of poly(3-thiopheneacetic acid) (PTAA) particles doped with perchloric acid. With increase in applied stress, these suspensions exhibit an evolution from a linear viscoelastic response, with three components of instantaneous elastic strain, retarded elastic strain and viscous strain, to a nonlinear viscoelastic response, where the retarded elastic and viscous strains monotonically decrease and a plastic contribution to the instantaneous strain grows, followed by a viscoplastic solid behavior, with fully plastic instantaneous strain, and finally a transition from plastic solid to a plastic liquid at the yield stress. With increase in electric field strength at fixed particle concentration and applied stress, the viscoplastic response diminishes, and more elastic behavior ensues. For highly doped samples, at high-electric field strengths, a fully elastic solid response is observed in the linear viscoelastic regime. The equilibrium compliance, J_C and steady state recoverable compliance J_R, were investigated as a function of electric field strength, particle concentration and particle conductivity. The results are interpreted in terms of the field-induced formation of thick fibrillar aggregates spanning the gap between the electrodes, each consisting of bundles of particle strings. Strings, which are fully connected to both electrodes generate an elastic response to the applied stress, whereas strings which are attached at only one end or are unattached generate a viscoplastic response. The net effect of an increase of the electric field strength, particle concentration, or particle conductivity is an increase in elasticity, i.e. predominantly creation of fully connected particle strings.     

Synthesis and characterization of superhydrophobic wood surfaces

Superhydrophobic films were developed on wood substrates with a wet chemical approach. Growth of zinc oxide (ZnO) nanorods was found differentially in the cross‐sectional walls and inner lumenal surfaces. The surface roughness of the prepared films on the inner lumenal surface conformed to the Cassie–Baxter wetting model, whereas the roughness across the microsurface of the cell wall was in conformity with the hydrophobic porous wetting model. The space between the ZnO nanorods and the microstructure of the wood surface constituted the nanoscale and microscale roughness of the ZnO nanofilm, respectively. The water contact angle of the prepared wood surfaces was up to 153.5°. In the prepared films, monolayers of stearic acid molecules were self‐assembled on the ZnO nanorods, which in turn, were attached to the wood surface via dimeric bonds. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on a terephthalic acid and dihydroxydiphenyl sulfone liquid crystalline copolymer and its composites with different thermoplastics

A liquid crystalline polymer (LCP) was synthesized by an interfacial polycondensation reaction at room temperature from terephthaloyl chloride and p,p′-dihydroxydiphenyl sulfone. The LCP synthesized was so stable and molecularly rigid that it did not show any phase transition until it degraded at about 320°C. Composites of the LCP with polycarbonate (PC), polystyrene (PS), and sulfonated polystyrene (SPS) were formed by compression molding at a temperature at which the thermoplastic matrix was in the melt state. They were thermally analyzed by differential scanning calorimetry. Tensile specimens were cut from the compression-molded plates, and mechanical tests were performed. The morphology of the material systems was studied by performing scanning electron microscopy analysis on cryogenically fractured specimens. For LCP/PS and LCP/SPS systems, a sharp two-phase morphology was formed, which suggested poor interfacial adhesion. The tensile strength of both systems decreased with LCP addition. The LCP/PC system also revealed a two-phase morphology; however, the interfaces between the LCP domains and the PC matrix were not so well defined, showing better interfacial adhesion than the two previous systems studied. Stronger bonding between the LCP and PC resulted in a significant improvement in the mechanical behavior of PC by LCP addition. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 645–652, 1997     

Cationic fluorene-thiophene diblock copolymers: Aggregation behaviour in methanol/water and its relation to thin film structures

Optical spectroscopy and photophysical measurements on cationic fluorene-thiophene diblock copolymers in solution show distinct properties for the two blocks, with clear indications of singlet exciton migration from the polyfluorene to polythiophene blocks. Electrical conductivity measurements and small angle X-ray scattering studies show that different aggregates are formed in water and methanol. This may be associated both with different solubilities of the two blocks and with the effect of solvent on the degree of dissociation of the ionic part. Atomic force microscopy (AFM) shows that different nanostructures are deposited from the two solvents, with large, vesicular structures deposited on mica from methanolic solution. Aggregation behavior is also found to be modulated, and to lead to more rigid thiophene blocks, by addition of the oppositely charged surfactant sodium dodecylsulfate.     

Immobilization of glucose oxidase and electron-mediating groups on the film of 3-methylthiophene/thiophene-3-acetic acid copolymer and its application to reagentless sensing of glucose

Enzyme electrodes were prepared by covalent immobilization of glucose oxidase (GOx) on the films of conducting copolymer obtained by electrochemical copolymerization of 3-methylthiophene and thiophene-3-acetic acid. Onto the enzyme electrodes, 2,5-dihydroxyphenyl (DHP) groups were introduced as redox mediators by the reaction of 2,5-dihydroxybenzaldehyde using alkylenediamines as linker molecules. The mediator-carrying enzyme electrodes were applied to reagentless glucose sensing system. It was found that response current to glucose was increased by introducing DHP groups, and the longer the alkylene chain of used alkylenediamine was, the higher the response current became. For a comparison, poly-l-lysine was linked onto the films of the conducting copolymer in advance, and immobilization of GOx and then introduction of DHP groups were carried out. The mediator-carrying electrode prepared thus gave higher amperometric response than those prepared with alkylenediamines, suggesting that amino groups of poly-l-lysine functioned effectively as the sites for binding GOx and DHP groups.     

Synthesis and property studies of linear and kinked poly(pyreneethynylene)s

A series of fluorescent conjugated polymers, poly(pyreneethynylene)s, have been designed and synthesized to investigate the effect of shape of polymer backbone on physical properties. Polymers with linear and kinked backbone were synthesized using 1,6- and 1,8-disubstituted pyrene. The target copolymers were designed to incorporate various spacer units, such as, alkoxyphenyl, carbazole and fluorene on the polymer backbone. Characterization of the target compounds was achieved by NMR, IR, GPC and MALDI-TOF mass spectrometry. Detailed investigation on their optical, electrochemical and thermal properties revealed significant contribution of the geometry of polymer backbone towards physical properties. Kinked backbone of cisoid-polymers was found to result in lower optical band gap, less negative E_HOMO and higher thermal stability as compared to their linear analogues, most probably due to the coiling of polymer chains. Comparison of the physical properties of the polymers with those of the model compounds suggested similar extent of conjugation through 1,6- and 1,8-position of pyrene.     

Architecture of nanostructured polymers by segregated domain crosslinking of block‐graft copolymer micelles

Polystyrene‐block‐polyisoprene (PS‐block‐PI; high 3,4‐structure) diblock copolymer was prepared by living anionic polymerization. For transfer into a reactive intermediate, the hydroxylation of the double bonds of PI block was achieved by hydroboration, followed by oxidation. Esterification of the hydroxy‐derivative with stearoyl chloride or decanoyl chloride resulted in block‐graft copolymers composed of PS (flexible chain)‐grafted long alkane (stretched chains). After partial chloromethylation of PS block copolymer, photofunctional N,N‐diethyldithiocarbamate (DC) groups were introduced into such pendant sites by reaction with the corresponding sodium salt. We studied the self‐assemblies of photofunctional block‐graft copolymers in a selective solvent, such as heptane, and constructed nanostructured polymers by crosslinking PS cores under UV irradiation. © 2001 Society of Chemical Industry     

Electrochemical synthesis and characterization of novel bile acid functionalized polypyrroles

A new series of pyrroles bearing bile acid moieties were synthesized and electrochemically polymerized in acetonitrile with tetrabutylammonium hexafluorophosphate (TBAFP₆) as the supporting electrolyte. It is found that these functionalized monomers could form polypyrrole films, but their electrochemical properties and the stability of the films are strongly dependent on the length of the alkyl spacer between pyrrole ring and the pendant bile acid moiety. Each of the resulting polymers with different bile acid groups shows a distinctive behaviour in terms of its microstructure of surface, as well as electrochemical and optical properties. Compared to other analogous polypyrroles, the optical property of the cholic acid functionalized polymer is sensitive to the polarity of the used solvents, exhibiting solvatochromic behaviour. This phenomenon is probably derived from its unique facial amphiphilic structure.     

Synthesis and optically acid-sensory properties of novel polyoxadiazole derivatives

New organo-soluble and blue-emissive fluorene-based polyoxadiazoles, PFO_x and PFO_xEH, exhibit colorimetric and fluorescent acid-sensory properties to a strong acid due to the weak basicity of imine-type nitrogen atom(s) in an 1,3,4-oxadiazole ring. To further investigate their protonation with an acid, ¹H NMR spectroscopy and AM1 semiempirical quantum-mechanics are utilized as well as UV-visible absorption and fluorescence spectroscopies. These investigations indicate the protonation does not proceed thermodynamically but kinetically at the initial stage of the complex formation of an acid and an oxadiazole ring in the polymer backbone.     

Synthesis of poly(p-phenylene vinylene) and derivatives via a new precursor route, the dithiocarbamate route

A new synthetic route towards poly(para-phenylene vinylene) (PPV) and its derivatives has been investigated. In this route, a bis-dithiocarbamate monomer is polymerized towards a dithiocarbamate precursor polymer by the addition of a strong base (LDA). The corresponding conjugated polymer is obtained via a heat treatment of the precursor polymer. This dithiocarbamate (DTC) precursor route strikes an optimal balance between several straightforward but sometimes troublesome precursor routes and the more complex sulphinyl precursor route yielding superior purity materials. The novelty lies in the fact that the monomer synthesis is not as difficult as compared to the sulphinyl route and this without losing the quality and accessibility of the precursor polymer. In the paper, the mechanism of the polymerization process is discussed and strong indications for radical as well as anionic mechanisms are presented.     

Synthesis and properties of novel fully conjugated polymers containing bithiazole rings

Two novel fully conjugated polymers containing bithiazole rings (PDDBTz and PDABTz) were first synthesized by polycondensation of 2,7-dimethyl-2,4,6-octatriene-1,8-dial with 2,2′-bis(diethylphosphinatyl methyl)-4,4′-bithizole or 2,2′-diamino-4,4′-bithiazole (DABT). The structure of the polymers was determined by IR, ¹H NMR and elemental analysis. PDDBTz is soluble in trifluoroacetic acid and DMSO, whereas PDABTz is soluble in common solvent such as THF, DMSO, DMF. Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions. Their lanthanide metal complexes were prepared. The magnetic behavior of these polymeric complexes was measured as a function of magnetic field strength (0-60 kOe) at 4 K and as a function of temperature (4-300 K) at magnetic field strength of 30 kOe. The results show that they all exhibit features of soft ferromagnet.     

Preparation of organic/inorganic hybrid nanomaterials using aggregates of star block copolymer consisting of poly(stearyl methacrylate) and poly(3‐(trimethoxysilyl) propyl methacrylate) as precursor

A series of star block copolymer consisting of poly(stearyl methacrylate) and poly(3‐(trimethoxysilyl)propyl methacrylate) was synthesized via atom transfer radical polymerization technique. The resultant polymers were characterized by gel permeation chromatography and ¹H NMR. The copolymer can self‐assemble into the aggregates in selective solvents, the resulting aggregates can be used as precursor to prepare hybrid nanomaterials conveniently via the hydrolysis reaction of ? Si(OCH₃)₃ groups and the condensation reaction of ? Si(OH)₃ groups. Moreover, the effect of the star copolymer‐solvent interaction on the aggregation behavior was also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007