Synthesis,characterization, and photophysical properties of novel poly(p‐phenylene vinylene) derivatives with conjugated thiophene as side chains

Two novel poly(p‐phenylene vinylene) (PPV) derivatives with conjugated thiophene side chains, P1 and P2, were synthesized by Wittig‐Horner reaction. The resulting polymers were characterized by ¹H‐NMR, FTIR, GPC, DSC, TGA, UV–Vis absorption spectroscopy and cyclic voltammetry (CV). The polymers exhibited good thermal stability and film‐forming ability. The absorption spectra of P1 and P2 showed broader absorption band from 300 to 580 nm compared with poly[(p‐phenylene vinylene)‐alt‐(2‐methoxy‐5‐octyloxy‐p‐phenylene vinylene)] (P3) without conjugated thiophene side chains. Cyclic voltammograms displayed that the bandgap was reduced effectively by attaching conjugated thiophene side chains. This kind of polymer appears to be interesting candidates for solar‐cell applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hyperbranched polymer for light‐emitting applications

A light‐emitting partially conjugated hyperbranched polymer (2,5‐dimethoxy‐substituted hyperbranched poly(p‐phenylene vinylene), MOHPV) based on rigid fluorescent conjugated segments, 2,5‐dimethoxy‐substituted distyrylbenzene (a derivative of oligo‐poly(p‐phenylene vinylene)), and flexible non‐conjugated spacers, trioxymethylpropane, was synthesized via an A₂ + B₃ approach. The weight‐average molecular weight was 2.48 × 10⁴ g mol^?1. The introduction of two methoxy groups into central rings of the oligo‐poly(p‐phenylene vinylene) imparted to MOHPV better solubility in common organic solvents and processability than its analogues reported in our previous work, especially the fully conjugated hyperbranched polymers. The effect of the molar ratio of monomer A₂ to monomer B₃ on the molecular weight and molecular weight distribution was investigated. A single‐layer light‐emitting diode was fabricated employing MOHPV as an emitter. A double‐layer light‐emitting diode was also fabricated by doping an electron transport material, 2‐(4‐biphenylyl)‐5‐phenyl‐1,3,4‐oxadiazole, into the emitting layer and inserting a thin layer of tri(8‐hydroxyquinoline)aluminium as electron‐transporting/hole‐blocking layer. A maximum luminance of 1500 cd m^?2 at 12 V and a maximum electroluminescence efficiency of 1.38 cd A^?1 at 14 mA cm^?3, which are approximately 43.5 and 12.9 times greater, respectively, than those of the single‐layer device, were achieved. The synthetic simplicity, excellent solubility and solution processability, and less of a propensity to aggregation make MOHPV a novel type of emitter for polymer light‐emitting displays. Copyright © 2010 Society of Chemical Industry     

Novel porphyrin‐grafted poly(phenylene vinylene) derivatives: Synthesis and photovoltaic properties

A series of novel porphyrin‐grafted poly (phenylene vinylene) derivatives, Porp‐RO‐PPV, were synthesized by a simple two‐step method. These copolymers contain conjugated poly(phenylene vinylene) derivatives as polymer backbone and covalently linked porphyrin units as side chain, which were confirmed by FTIR and ¹H NMR, and used for photovoltaic devices. The thermal, optical properties and sensitizing effect, and photovoltaic properties have been investigated. The emission spectra of Porp‐RO‐PPV copolymers revealed the existence of strong energy transfer from PPV backbone to porphyrin units. The energy conversion efficiency (η_e) of photovoltaic devices based on Porp‐RO‐PPV+PCBM reached 0.33% (78.2 mW/cm², AM1.5) and porphyrin units in the copolymers showed good sensitizing effect at low concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymeric coatings for photostability enhancement of poly(p‐phenylene vinylene) derivative films

Poly(p‐phenylene vinylene) (PPV) derivatives are an important class of conjugated polymers, known for their applications as electroluminescent materials for light‐emitting devices and sensors. These derivatives are highly susceptible to photodegradation by the combined action of oxygen and light. Here, the use of various commercial polymers as protective coatings against the photodegradation of PPV derivatives was explored. Cast films of two similar PPV derivatives, poly[(2‐methoxy‐5‐n‐hexyloxy)‐p‐phenylene vinylene] and poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐p‐phenylene vinylene], were submitted to photodegradation by exposure to white light under atmospheric conditions in order to verify if the type of side chain (linear or branched) had an effect on the photodegradation. No significant differences in the photodegradation behaviour between the two polymers were noticed. The following commercial polymers were tested as protective coatings for the PPV derivative cast films: 99 and 80% hydrolysed poly(vinyl alcohol) (PVA) and starch. The best results were achieved using coatings of 99% hydrolysed PVA, which increased about 700 times the time necessary for complete degradation of the PPV derivative films. The results show the effectiveness of this coating in minimizing and, possibly, controlling the effects of the photodegradation of PPV derivative films, which can be useful in many applications, e.g. oxygen sensors. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of novel soluble alternating copoly(phenylene vinylene) derivative for light‐emitting electrochemical cell

A novel alternating copolymer, poly{[2,5‐di(2‐(2‐ethoxy ethoxy)ethoxy)‐1,4‐phenylene vinylene]‐alt‐1,4‐[phenylene vinylene]}, has been synthesized through the Wittig condensation as electroluminescent material. In this copolymer, one component is phenylene vinylene with flexible oligo(ethylene oxide) side chain that facilitates ion transportation and phase miscibility between nonpolar and polar part of composite luminescent layer, and another is a rigid phenylene vinylene moiety to improve luminescent quantum efficiency and tune color. The copolymer shows good solubility and thermal stability for device fabrication compared to poly(phpeylene vinylene)(PPV). The band gap value of copolymer is between those of corresponding homopolymers, which indicates that alternating copolymerization is a suitable way to obtain luminescent polymer with desired band gap. The maximum wavelength of photoluminescence of copolymer is 539 nm (yellowish‐green). The HOMO and LUMO energy levels obtained by cyclic voltammetry measurement indicate that the electron injection ability of copolymer has been greatly improved compared with that of the PPV. A more balanced carrier injection and higher quantum efficiency are proved by electroluminescent properties of corresponding light‐emitting devices. The turn‐on voltage of LEC device (ITO/copolymer + PEO + LiClO₄/Al) is found to be 2.3 V, with current comparative to LED (ITO/copolymer/Al) at 9.5 V. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1350–1356, 2003     

Electroluminescence and photovoltaic properties of poly(p‐phenylene vinylene) derivatives with dendritic pendants

A copolymer of dendronized poly(p‐phenylene vinylene) (PPV), poly{2‐[3′,5′‐bis (2′‐ethylhexyloxy) bnenzyloxy]‐1,4‐phenylene vinylene}‐co‐poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene] (BE‐co‐MEH–PPV), was synthesized with the Gilch route to improve the electroluminescence and photovoltaic properties of the dendronized PPV homopolymer. The polymer was characterized by ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, and electrochemical cyclic voltammetry and compared with the homopolymers poly{2‐[3′, 5′‐bis(2‐ethylhexyloxy) benzyloxy‐1,4‐phenylene vinylene} (BE–PPV) and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH–PPV). Polymer light‐emitting diodes based on the polymers with the configuration of indium tin oxide (ITO)/poly(3,4‐ethylene dioxythiophene) : poly(styrene sulfonate) (PEDOT : PSS)/polymer/Ca/Al were fabricated. The electroluminescence efficiency of BE‐co‐MEH–PPV reached 1.64 cd/A, which was much higher than that of BE–PPV (0.68 cd/A) and a little higher than that of MEH–PPV (1.59 cd/A). Photovoltaic properties of the polymer were studied with the device configuration of ITO/PEDOT : PSS/polymer : [6,6J‐phenyl‐C₆₁‐butyric acid methyl ester] (PCBM)/Mg/Al. The power conversion efficiency of the device based on the blend of BE‐co‐MEH–PPV and PCBM with a weight ratio of 1 : 3 reached 1.41% under the illumination of air mass 1.5 (AM1.5) (80 mW/cm²), and this was an improvement in comparison with 0.24% for BE–PPV and 1.32% for MEH–PPV under the same experimental conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Branched poly(p‐phenylenevinylene): Synthesis,optical and electrochemical properties

A series of poly(p‐phenylene vinylene) (PPV) derivatives with phenylene vinylene side chains (branched PPVs), PPV0, PPV1, PPV2, and PPV3, were synthesized by the Heck coupling reaction and characterized by TGA, absorption spectra, photoluminescence (PL) spectra, and electrochemical cyclic voltammetry. The branched PPVs showed two absorption peaks in the UV–vis region, corresponding to the conjugated side chains (UV absorption) and the main chains (the visible absorption). Especially the absorption spectrum of PPV3 covers a broad wavelength range from 300 to 500 nm. Introducing the electron‐donating alkoxy substituents on the PPV main chains and increasing the content of the alkoxy groups lead to bathochromic shift of both absorption and PL spectra from PPV1 to PPV2 to PPV3. The onset oxidation potential of the branched PPVs is lower by 0.1–0.2 V than that of PPV, indicating that the electron‐donating ability of the branched PPVs enhanced in comparison with that of PPV. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Electrical properties of poly(p‐phenylene vinylene) films with an incorporation of platinum metal nanoparticles

The effects of platinum metal nanoparticles on a conjugated polymer were investigated by monitoring the electronic structures and measuring the electrical properties of poly(p‐phenylene vinylene) (PPV) and PPV/Pt nanocomposites films. Enhanced current density in PPV/Pt nanocomposite films was obtained by the incorporation of Pt nanoparticles into the conjugated polymer PPV. This result agrees well with our observation of an increase in the electron affinity and an increase in roughness with increasing Pt nanoparticle content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The preparation and characterization of high‐performance and thermally stable electroluminescent poly(p‐phenylene‐vinylene‐b‐oligoethylene oxide)

Two luminescent block copolymers (PPVPEO₂₀₀ and PPVPEO₆₀₀), composed of poly(p‐phenylene‐vinylene) (PPV) segments with three phenylene vinylene units and poly(ethylene oxide) (PEO) segments with molecular weight of 200 and 600, respectively, have been successfully synthesized. The structures of the copolymers were verified using FTIR, ¹H‐NMR, and elemental analysis. Single‐layer polymer light‐emitting electrochemical cells (LEC) devices fabricated on the bases of thin films of PPVPEO₆₀₀ and on the bases of thin films of blends of PPVPEO₂₀₀ with additional PEO both demonstrated good electroluminescent (EL) performance with the onset voltage of 2.6 V and EL efficiency of 0.64 cd/A and 0.68 cd/A at 3.2 V, respectively. Thermal analysis shows that the decomposition temperature of PPVPEO₆₀₀ is about 305°C, which is higher than that of PPVPEO₂₀₀ and PEO. AFM studies of PPVPEO₆₀₀ thin films exhibits that the block copolymer self‐assembles to form nanoscale network structures with pseudo‐cross‐linking points, thus accounting for its high thermal stability and good EL performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1118–1125, 2007     

Preparation and characterization of thin films of the poly(p‐phenylene vinylene) semiconducting polymer

Conjugated polymers have been the subject of many studies because of their widespread applications in electronic and optoelectronic devices. Poly(p‐phenylene vinylene) is a leading semiconducting polymer in optical applications. This work is focused on the development of thin films of poly(p‐phenylene vinylene) by spin coating and their characterization with Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy to understand their changes. An empirical model has been developed to show the effect of the variables—the spin speed, polymer concentration, and spin time—on the film thickness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Synthesis and properties of partially conjugated hyperbranched light‐emitting polymers

Via A₂ + B₄ and A₂ + B₃ [where A₂ is 1,4‐distyrylol‐2,5‐butoxybenzene, B₃ is 1,1,1‐tris‐(p‐tosyloxymethyl)‐propane, and B₄ is pentaerythritol tetra(methyl benzene sulfonate)] approaches, we synthesized two kinds of partially conjugated hyperbranched polymers, hyperbranched polymer with 3 arms (HP1) and hyperbranched polymer with 4 arms (HP2), which had rigid conjugated segments [oligo‐poly(phenylene vinylene)] and flexible, nonconjugated spacers arranged alternately through ether bonds in the skeleton. The conjugated segments were modified by pendant butoxy groups, which imparted the resulting polymers with excellent solubility in common organic solvents and excellent film‐forming abilities. Fourier transform infrared and nuclear magnetic resonance spectroscopy were used to identify the structure of the monomers and polymers. Thermal property investigations showed that two polymers both had good thermal stability with their decomposition temperatures in the range 396–405°C and high glass‐transition temperatures, which are of benefit to the fabrication of high‐performance light‐emitting devices. The photophysical properties were studied, and the relative photoluminescence quantum efficiencies of HP1 and HP2 in dilute chloroform solution amounted to 56.8 and 49.3%, respectively. A brief light‐emitting diode device with a configuration of indium tin oxide/HP1/Ca/Al was fabricated, and its electroluminescence performance was studied. The brightness of the device reached an optimistic maximum of 190 cd/m² at 8.2 V. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Conjugated copolymers of cyanosubstituted poly(p‐phenylene vinylene) with phenylene ethynylene and thienylene vinylene moieties: Synthesis,optical, and electrochemical properties

Three alternating conjugated copolymers of cyanosubstituted poly(p‐phenylene vinylene) (CN–PPV) with phenylene ethynylene and thienylene vinylene moieties, P1, P2, and P3, were synthesized via cross‐coupling polycondensation with Pd(PPh₃)₂Cl₂ as a catalyst. Their structures were confirmed by ¹H‐NMR, IR spectroscopy, elemental analysis, and gel permeation chromatography, and the thermal, photophysical, and electrochemical properties of the copolymers were also investigated. The incorporation of a triple bond into the CN–PPV backbone led to higher reduction potentials, which corresponded to lower lowest unoccupied molecular orbital energy levels. The three copolymers possessed broader absorption spectra, especially copolymer P3 with its polymerization units containing two thiophene rings, which showed the broadest absorption spectrum, from 300 to 710 nm. Their high electron affinities, broad absorptions, and relatively higher oxidation potentials make the copolymers potentially good electron‐acceptor material for use in photovoltaic devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of poly(fluorene vinylene) copolymers containing thienylene–vinylene units

Narrow‐band‐gap 2,5‐thienylene‐divinylene (ThV) units were incorporated into the poly(fluorene vinylene) backbone via a Gilch reaction as an energy trap with various feed ratios; this yielded pronounced changes in the electrochemical and optical properties of the material. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the polymers {poly(9,9‐di‐iso‐octylfluorene vinylene) [poly(fluorene vinylene‐co‐thiophene vinylene (FV))], C1, and C2 } were estimated to be ?5.53 to ?5.10 eV and ?2.98 to ?2.84 eV, respectively, by cyclic voltammetry measurements. In comparison with poly(FV), the HOMO energy levels of polymers poly(fluorene vinylene‐co‐thiophene vinylene (FV) (90 : 10) ( C1 ) and poly(fluorene vinylene‐co‐thiophene vinylene (FV) (80 : 20) ( C2 ) were significantly increased, but their LUMO energy levels were slightly decreased. The optical properties were investigated by absorption and emission spectra of the polymers. The good spectral overlap between the emission of poly(FV) and the absorption of polymers C1 and C2 revealed a sufficient energy transfer from the majority of 9,9‐di‐iso‐octylfluorene vinylene units to the minority of ThV units. The reduction of self‐absorption losses of polymers C1 and C2 due to spectral separation caused by the incorporation of ThV units could be indirectly confirmed by nonlinear optical (NLO) properties. The result of the NLO properties of the polymers showed that the third‐order NLO coefficients of poly(FV), C1, and C2 were 8.1 × 10^?10, 1.35 × 10^?9, and 1.51 × 10^?9 esu, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of photoluminescent conjugated polymer containing N‐(α‐naphthyl)‐carbazole unit

A novel luminescent conjugated polymer, poly[{9‐(α‐naphthyl)‐3,6‐divinylenecarbazolylene}‐alt‐co‐(1,4‐phenylene)] (PNVCP), bearing alternated 9‐(α‐naphthyl)‐carbazole and benzene units, was synthesized via a Wittig–Horner reaction. The solubility, thermal, and optical properties were investigated. It was soluble in common organic solvents, such as tetrahydrofuran and 1,2‐dichlororoethane. Thermogravimetric analysis and differential scanning calorimetry showed that the conjugated polymer exhibited good thermal stability up to 496°C with a glass‐transition temperature higher than 110°C. The photoluminescence properties were studied. The polymer emits blue light and the quantum yield is 93% in solution. The emission spectra exhibited an obvious solvent effect. With the increase of the polarity of the solvents, the fluorescence spectra changed obviously and appeared to be redshifted at room temperature. The redshift was more obvious in aromatic solvents than in aliphatic solvents. When N,N‐dimethylaniline was gradually added into the solution of the conjugated polymer, the emission intensity of the fluorescence decreased. In comparison, the emission intensity of the polymer showed invariability when 1,4‐dicyanobenzene was added into the polymer solution. Moreover, the fluorescence of the polymer could be effectively quenched by fullerene. Overall, the synthesized polymer is a potential candidate material for fabrication of polymeric light‐emitting devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 923–927, 2006     

Synthesis,photo‐, and electroluminescent properties of the soluble poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐ 4,4′‐vinylene]

A novel soluble conjugated polymer, poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐4,4′‐vinylene] (O‐PPV), containing an electron‐transporting group on the main chain of PPV, was synthesized according to HORNER mechanism. The oligo‐polymer with M_w = 1000 and T_d = 270°C is soluble in chloroform and tetrahydrofuran. The photoluminescent (PL) properties were investigated using different concentrations of solid‐state O‐PPV/PEO blends absorption and selective excitation measurements. The results show that PL arises from interchain charge‐transfer states in solid‐state O‐PPV. Compared with the analogous single‐layer device constructed with PPV (ITO/PPV/Al), which emits two peaks at λ = 520 nm and 550 nm (shoulder), the electroluminescence (EL) spectrum of the device [ITO/O‐PPV (80 nm)/Al] is a broad peak at λ_max = 509 nm. The quantum efficiency (0.13%) of the device ITO/O‐PPV/Al is much higher than that of the device ITO/PPV/Al, due to the introduction of the electron‐transporting group–oxadiazole units in the main chain of PPV. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3535–3540, 1999     

Synthesis and characterization of poly(2,5‐didecyl‐1,4‐phenylene vinylene), poly(2,5‐didecyloxy‐1,4‐phenylene vinylene), and their alternating copolymer

The preparation of dialkyl‐substituted poly(2,5‐didecyl‐1,4‐phenylene vinylene) ( PDDPV ) by the Horner‐Emmons polycondensation is described. Its performance in an organic light‐emitting diode (OLED) device architecture is compared with devices prepared from the analogous dialkoxy‐substituted poly(2,5‐didecyloxy‐1,4‐phenylene vinylene) ( PDOPV ) and the corresponding alkyl‐alkoxy‐substituted alternating copolymer. Additionally, the structure, stability, electrochemical, and optical properties of the PPVs were characterized by gel permeation chromatography, thermogravimetric analysis, NMR spectroscopy, cyclic voltammetry, UV‐Visible spectroscopy, and fluorescence spectroscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41162.     

Synthesis,photophysical properties and microphase separation of all‐conjugated diblock copolymers with hydrophilic side chains

A series of new all‐conjugated diblock copolymers, poly(2,5‐dioctyloxy‐p‐phenylene)‐block‐poly(3‐methoxyethoxyethoxy‐methylthiophene) (PPP‐b‐P3MEEMT), with hydrophilic side‐chains have been synthesized by quasi‐living Grignard metathesis polymerization. The narrow polydispersity indices of the block copolymers are in the range 1.32–1.40. The block ratios in the obtained diblock copolymers can be well defined by the feed ratios of the monomers. Photoluminescence results reveal that resonance energy transfer occurs from the PPP block to the P3MEEMT block in dilute solution. Differential scanning calorimetry shows that both PPP and P3MEEMT blocks in the copolymers produce crystalline regions and lead to microphase separation as indicated by two endothermal transitions, corresponding to the melting peaks of the PPP and P3MEEMT blocks, respectively. The formations of microphase‐separated nanostructures in annealed copolymer films are also observed using transmission electron microscopy. © 2012 Society of Chemical Industry     

Enhancement of the electrical properties of poly(p‐phenylene vinylene) by the incorporation of silicon dioxide nanoparticles

The electrical properties of a poly(p‐phenylene vinylene) (PPV) conjugated polymer using silver (Ag) as a cathode were improved by the incorporation of silicon dioxide (SiO₂) nanoparticles. The current density of the Ag–PPV/SiO₂ nanocomposite system was higher than that of Ag–PPV. A lower level of interfacial oxidation was found in the Ag–PPV/SiO₂ nanocomposite than in Ag–PPV, confirming that a more complete elimination of residue occurred in the nanocomposite. This was due to the relatively large surface area of the PPV/SiO₂ nanocomposite film and the hydrophilic surface of the SiO₂ nanoparticles. The lower level of oxidation contributed to an improvement in the material's current–voltage characteristics. Morphology‐dependent current–voltage characteristics were enhanced by a large variation in the thickness of the Ag–PPV/SiO₂ nanocomposite film because an increased effective field strength could be induced in the thinner regions of the film. The incorporation of SiO₂ nanoparticles altered the effective film thickness and the amount of residue in the interior of the PPV without disrupting the structure of the conjugated polymer. The Ag cathode created a stable interface with the PPV film layer without causing the formation of an organic–metal complex, which would have obstructed electron injection. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010