Preparation of polystyrene/poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] fluorescent microspheres by miniemulsion polymerization

Fluorescent microspheres have great potential for use as probes in biological diagnostics. In this context, poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV), a conjugated polymer which has high quantum yield, controllable emitting wavelength and facile processing in manufacture, was used as a fluorescent material for the preparation of polystyrene (PS)/MEH‐PPV fluorescent microspheres via miniemulsion polymerization. We demonstrate that the emitting wavelength of the PS/MEH‐PPV fluorescent microspheres can be regulated by changing the amount of azobisisobutyronitrile initiator in the polymerization process. Using acrylic acid comonomer, poly[styrene‐co‐(acrylic acid)]/MEH‐PPV fluorescent microspheres with functional carboxyl groups were also prepared. All the microspheres were characterized using transmission electron microscopy, scanning electron microscopy, fluorescence microscopy and fluorescence spectrophotometry. The functional carboxyl groups were characterized using Fourier transform infrared spectroscopy. This work provides a novel platform for the preparation of conjugated polymer fluorescent microspheres for biological applications. © 2012 Society of Chemical Industry     

Enhancing the electroluminescence properties of novel blue light emitting polymer and MEH‐PPV based white light emitting polymer devices by processing condition optimization

A series of triarylaminooxadiazole‐containing tetraphenylsilane light emitting polymer (PTOA) and poly(2‐methoxy, 5‐(2′‐ethyl‐hexyloxy)‐p‐phenylene‐vinylene) (MEH‐PPV) based white light emitting polymer devices (PLEDs) were fabricated to study blue and orange–red emitter composition and light emitting layer processing effects on white emission electroluminescence properties. Color purity, current turn‐on voltage, brightness, and current efficiency were strongly determined by MEH‐PPV content and the thin film processing condition. The intensity of PTOA blue emission was equal to that of MEH‐PPV orange–red emission when the device was fabricated by a polymer composite film containing 10 wt % of MEH‐PPV. Color purity [Commission Internationale de L'Eclairage (CIE_x,y) coordinates (0.26,0.33)] was nearly white emission under applied 8 V. The brightness and current efficiency of PTOA‐MEH‐PPV composite film based devices increased as MEH‐PPV content increased. Furthermore, white emission blue shifted with increasing spin‐rate of thin film coating and applied voltage. Low turn‐on voltage, high current density, and high brightness were obtained for the device fabricating with light emitting layer coating with high spin‐rate. Moreover, low current efficiency was obtained for the PLED with a thinner light‐emitting layer. A white emission CIE (0.28,0.34) was obtained for PTOA‐MEH‐PPV based white PLED. White PLED brightness and efficiency can be as high as 700 cd/m² and 0.78 cd/A, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Polychromatic light‐emitting conjugated polymer prepared by controlling its structure through active free radical addition

BACKGROUND: The HOMO–LUMO energy level width of conjugated polymers can be manipulated by controlling the conjugation length of the polymeric materials in order to adjust their properties in terms of emission of different colors and realize polychromatic displays. In the work reported in this paper azobisisobutyronitrile (AIBN) was used to control the conjugation length of poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐co‐(1,4‐phenylene vinylene)] (MEH‐PPV) by free radical addition. In this way a series of MEH‐PPV with various conjugation lengths was obtained. RESULTS: Characterization of MEH‐PPV using ¹H NMR and Fourier transform infrared spectroscopy demonstrated that the cyano groups of AIBN hydrolyzed into carboxyls. The carboxyl free radicals attacked the conjugated double bonds of MEH‐PPV, resulting in a decrease of trans‐vinylenes and in an increase of cis‐vinylenes as well as tert‐methyls on the backbone. Changing the conjugated structure of the polymer caused the peaks of UV and fluorescence spectra to shift to the blue. CONCLUSION: The resulting MEH‐PPV derivatives can emit orange‐red, green and blue light. It is expected that they could be used to prepare PPV‐based materials that could modulate white light emission, by simply blending the PPV derivatives emitting different colors. Copyright © 2008 Society of Chemical Industry     

Self‐organized MEH‐PPV domains in a TPU matrix and the consequences to the luminescence spectra

Self‐sustained cast films formed from heterogeneous blends of poly(2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV) conjugated polymer and thermoplastic polyurethane (TPU) were investigated by photoluminescence (PL) and scanning electron microscopy (SEM). A blue shift is observed for the pure electronic transition PL peak (E₀₀) with decreasing MEH‐PPV concentration. The two clear shoulders in the PL spectra at higher energy than the E₀₀ peak appear due to the formation of small conjugation segments of the MEH‐PPV molecules at the interface of the spherical MEH‐PPV domains. This assumption and the origin of the blue shift were confirmed by correlating the average size of the MEH‐PPV domains, observed from SEM images, and the analysis of the PL spectra at low temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Hyperbranched conjugated polymers for photovoltaic applications

Three hyperbranched phenylene vinylenes (HPVs)—H‐mn, H‐es, and H‐py—were used in fabricating polymer photovoltaic cells (PVCs). PVCs with photoactive layers composed of pure HPV, a blend of HPV and C₆₀, and a blend of HPV, poly(2‐methoxyl‐5,2′‐ethylhexyoxyl‐1,4‐phenylene vinylene) (MEH‐PPV), and C₆₀, were fabricated, and their current–voltage characteristics were measured and investigated. The PVC with photoactive layers composed of H‐es and C₆₀ showed promising photovoltaic characteristics, with an energy‐conversion efficiency of 0.035%, when illuminated under 85 mW/cm² white light. The short‐circuit current and energy‐conversion efficiency of the PVCs based on H‐mn/C₆₀ and H‐py/C₆₀ were greatly improved when they were blended with a small amount of MEH‐PPV. The incident photon‐to‐collected‐electron efficiency of the HPV/MEH‐PPV/C₆₀ PVCs indicated that both HPVs and MEH‐PPV contributed to the photocurrent. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1459–1466, 2004     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Origin of the methylene bonds in poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylenevinylene] prepared according to Gilch's method: novel applications

Impurities containing methylene bridges between 2‐((2′‐ethylhexyl)oxy)‐5‐methoxy‐benzene molecules are inevitably formed during the synthesis of 1,4‐bis(chloromethyl)‐2‐((2′‐ethylhexyl)oxy)‐5‐methoxy‐benzene, the monomer used in the preparation of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylenevinylene] (MEH‐PPV), but they can be removed by double recrystallization of the monomer prior to polymerization. When impurities containing methylene bridges participate in a Gilch polymerization, the methylene bonds formed in the main chains are prone to break at 200 °C, that is, at least 150 °C below the major degradation temperature of defect‐free MEH‐PPV. Interestingly, the thermal treatment used to break the methylene bonds present reduces the chain aggregation of MEH‐PPV during film formation and induces its blends with poly(2,3‐diphenyl‐5‐octyl‐p‐phenylene‐vinylene) (DPO‐PPV) to form a morphology similar to that of block copolymers. Both significantly enhance the luminescence properties. Copyright © 2006 Society of Chemical Industry     

Thermal degradation kinetics and lifetime prediction of a luminescent conducting polymer

The thermal stability, degradation kinetics and lifetime‐prediction of a luminescent conducting polymer, poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH‐PPV), are investigated. The derivative thermogravimetry curves indicate a double‐stage decomposition process in a nitrogen atmosphere, and a multi‐stage decomposition process in an air atmosphere. The apparent activation energy values of MEH‐PPV are higher in nitrogen than in air. Activation energies slightly increase and are then approximately stable in nitrogen for the initial mass loss, while the activation energy changes differently with the percentage mass loss in air. The activation energy decreases for the initial mass loss and increases with mass loss when the mass loss is above 30%; beyond 70% it decreases again. The lifetime of MEH‐PPV decreases dramatically from 10⁶ min to 0.03 min as the temperature increases from 25 °C to 300 °C in air. The lifetime is longer in nitrogen than in air and decreases from 10¹⁴ min to 2.34 min with increasing the temperature from 25 °C to 300 °C in nitrogen. These lifetime parameters indicate that the service/process temperature has a strong influence on the luminescence of MEH‐PPV. The maximum absorption and wavelength at maximum absorption of MEH‐PPV decrease with increasing temperature in the visible region. Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of poly(1,4‐phenylenevinylene) derivatives containing liquid crystalline oxadiazole groups

Two novel poly(1,4‐phenylenevinylene) (PPV) derivatives containing liquid crystalline oxadiazole side chains were prepared by a dehydrochlorination process. The homopolymer poly(2‐methoxy‐5‐((2‐methoxy‐phenyl)‐5‐hexyloxy‐phenyloxy‐1,3,4‐oxadiazole)‐1,4‐phenylenevinylene) (HO–PE₆) is insoluble in common solvents, whereas the copolymer poly(2‐methoxy‐5‐((2‐methoxy‐phenyl)‐5‐hexyloxy‐phenyloxy‐1,3,4‐oxadiazole))‐(2‐methoxy‐5‐(2′‐ethylhexyloxy))‐1,4‐phenylenevinylene) (CO–PE₆) is soluble in common solvents such as chloroform, THF, and p‐xylene. The molecular structure of CO–PE₆ was confirmed by FTIR, ¹H‐NMR, UV–vis spectroscopy, and polarized light microscopy. CO–PE₆ showed a maximum emission at 556 nm in chloroform and at 564 nm in solid film, when excited at 450 nm. The maximum electroluminescence emission of the device indium–tin oxide (ITO)CO–PE₆/Al is at 555 nm. The turn‐on voltage of LEDs based on CO–PE₆ and MEH–PPV is 6.5 and 8.5 V, respectively. The electron mobility of CO–PE₆ is higher than that of MEH–PPV based on the results of current–voltage and electrochemical behavior of both MEH–PPV and CO–PE₆. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 396–403, 2004     

Synthesis and spectroscopic and photoconduction characteristics of coaxial poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)−1,4‐phenylene vinylene] single‐walled carbon nanotube films with ohmic‐like transport attributes

Highly luminescent, core–shell, single‐walled carbon nanotube–poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)?1,4‐phenylene vinylene] (MEH‐PPV) one‐dimensional networks were synthesized by a multicycle unstable micellization method. The current–voltage data indicated that the charge transport within the nanowire network remained Ohmic, with the differential conductance scaling linearly with temperature in the temperature range of about 120 to 300 K. Further analysis based on the comparative study involving photoluminescence and Raman spectroscopic tests pointed to interchain interactions and nanotube–polymer interface as primary factors influencing the electronic characteristics of the processed samples. Likewise, steady‐state photoconduction tests confirmed that the heterointerface played a dominant role behind the increased photoresponse induced by exciton annihilation at a low bias regime. The study helped us identify the underlying physical mechanisms that controlled the optical, electrical, and photoconduction properties of the MEH‐PPV–carbon nanotube heteronetworks. Potentially, this will open a door to the development of next generation, low‐cost, all‐organic nanooptoelectronic devices and systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40029.     

Effects of a tert‐butylphenylene substituent on the structure and optical,fluorescent and thermal properties of the poly(p‐phenylenevinylene) derivatives

Two soluble fluorescent polymers, poly(2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylenevinylene) (DtBP‐PPV) and poly(2‐decyloxy‐1,4‐phenylenevinylene) (DO‐PPV), were prepared by a method similar to the Gilch procedure. The DtBP‐PPV and DO‐PPV have a same chemical structure except for the conjugated tert‐bytulphenyl substituents in the former. The polymers are characterized by using ¹H NMR, FTIR, UV–vis, photoluminescence (PL), and electroluminescence (EL) spectroscopies and thermogravimetric analysis (TGA). The ¹H NMR spectra show no tolane‐bis‐benzyl (TBB) structure defects in DtBP‐PPV but some in DO‐PPV. Both UV–vis absorption and PL emission peaks of the DtBP‐PPV exhibit a red‐shift phenomenon as compared with those of the DO‐PPV. Moreover, with the DtBP‐PPV and DO‐PPV acting as light‐emitting polymers separately, EL devices were fabricated with a sequential lamination of ITO/PEDOT/DtBP‐PPV (or DO‐PPV)/Ca/Ag. The DtBP‐PPV‐based device shows a lower turn‐on voltage, a longer EL emission wavelength, and a higher brightness than the DO‐PPV‐based device. The maximum brightness of DtBP‐PPV‐based device is 57 cd/m² at an applied voltage of 12 V. POLYM. ENG. SCI., 47:1380–1387, 2007. © 2007 Society of Plastics Engineers     

Fast response single‐ion transport light‐emitting electrochemical cell based on PPV derivative

We present the electrical and optical characteristics of a single‐ion transport light‐emitting electrochemical cell (SLEC) based on poly(p‐phenylene vinylene) (PPV) derivative containing aryl‐substituted oxadiazole in the backbone (MEH‐OPPV). Ionized polyurethane–poly(ethylene glycol) (PUI) used as polymer electrolyte is introduced into the active layer of the SLEC. The turn‐on voltage of the SLEC is about 3 V according to its current density–voltage (J–V) characteristics. The response time of the SLEC is less than 10 ms, lower than that of normal LECs by two orders of magnitudes roughly. The reasons of the quick response for the SLEC are discussed in the article. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4253–4255, 2006     

Phosphor‐in‐fluorescent‐glasses for high color rendering white light emitting diodes

Fluorescent glass frits were prepared and used to synthesize phosphor‐in‐fluorescent glass composites (PiFGs) to realize stable white light emitting diodes with high color‐rendering properties. Commercial red, green, and blue phosphors were co‐sintered and red phosphors were partially replaced by Eu³⁺ in glass frits. Phosphor‐in‐glass composites were placed on UV‐light emitting diodes (UV‐LEDs) to generate white light. Pure white light with a luminous efficacy=58.4 lm/W, general color rendering index R_a=87 and special color rendering index for strong red R₉=73 was realized with glass frits containing 7 mol% Eu₂O₃ and RGB ratio of 35:20:15. Luminous efficacy, R_a and R₉ increased as red phosphors were replaced by red‐fluorescent glass frits.     

Optical properties of MEH‐PPV conjugated polymer covered by silica nanoshells

Poly [2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylene vinylene] (MEH‐PPV) covered by nanostructured silica shells were synthesized via sol–gel process and investigated after freeze‐drying and heat‐drying in vacuum. The freeze‐dried sample consists of a light pink powder while the heat‐dried sample presents a redder coarse‐grained material. The freeze‐dried sample was analyzed using small angle X‐ray scattering (SAXS). Both samples were analyzed using photoluminescence (PL) and Raman spectroscopy at room temperature. The PL spectra presented relatively large red shifts compared with that of the MEH‐PPV in tetrahydrofuran solution, which was taken as a reference sample. The energy shifts observed in the PL and Raman spectra strongly support an explanation based on denser packing conditions inside the nanostructured silica shells, which can effectively lead the polymer molecules to a higher interchain interaction via aggregate sites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5620–5626, 2006     

Effect of thermal annealing in atmosphere on photoluminescence of BTEO–PPV films

The photoluminescence (PL) spectra of poly[2,5‐bis‐(tri‐ethoxy)‐1,4‐phenylene vinylene] (BTEO–PPV) films are blue‐shifted with increasing thermal annealing temperature. It is known from the UV–vis absorption spectra that thermal annealing decreases the conjugation length of the polymer. For BTEO–PPV films, unlike with MEH–PPV films, the symmetric triethoxy side groups further block aggregation of the polymer chains. The absorption Fourier transfer infrared spectra showed that thermal annealing in atmosphere destroyed the chain structure of BTEO–PPV film by thermal oxidation to form aldehyde groups, which resulted in low PL efficiency of the annealed films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis,characterization, and electro‐optical properties of a soluble conjugated polymer containing an oxadiazole unit in the main chain

A novel copolymer, poly{[2,5‐diphenylene‐1,3,4‐oxadiazole‐vinylene]‐alt‐[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene]}(MEH‐OPPV) containing a high‐electron‐affinity unit of aromatic oxadiazole in the main chain is synthesized through the Wittig condensation reaction. The obtained copolymer is easily soluble in conventional organic solvents. The structure of the copolymer was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and ultraviolet‐visible and photoluminescence spectroscopy. The TGA result indicates that the copolymer has very high thermal stability (stable up to 310°C in nitrogen), while DSC investigation demonstrates that the glass transition temperature (T_g) is 143°C, which might be a merit for the long‐life operation of light‐emitting devices. The absorption spectrum of film sample of the copolymer reveals two peaks at 310 and 370 nm, respectively, and the edge absorption corresponds to a band gap of 2.46 eV. A single‐layer light‐emitting diode device ITO/MEH‐OPPV/Al is successfully fabricated. The device emits visible yellowish‐green light above the bias voltage of 4.0 V under ambient condition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2618–2623, 2003     

Synthesis and light‐emitting properties of new poly(p‐phenylenevinylene) derivatives containing oxadiazole moiety

Two new poly(p‐phenylenevinylene) (PPV) derivatives containing oxadiazole moiety (OXA‐PPV1 and OXA‐PPV2) were synthesized by the Wittig condensation polymerization reaction. Their thermal and light‐emitting properties were investigated. The single‐ and triple‐layer electroluminescent (EL) devices with configurations of ITO/polymer/Al and ITO/polymer/OXD‐7/Alq₃/Al were fabricated. They exhibited blue emission at 470 nm for OXA‐PPV1 and green emission at 560 nm for OXA‐PPV2. The turn‐on voltages of triple‐layer device were 11 V for OXA‐PPV1 and 8 V for OXA‐PPV2. The triple‐layer EL devices showed much better performance than did the single‐layer devices. The spectra indicated energy transfer occurred from segments of side chain to polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 422–428, 2002     

Benefits of a high‐performance phosphite in the gamma irradiation of polyolefins

The highly active process stabilizer bis(2,4‐dicumylphenyl)pentaerythritol diphosphite (P1) was compared in a series of polyolefin formulations with tris(2,4‐di‐t‐butylphenyl) phosphite (P2). Because of its high activity, there was less polymer degradation during processing with P1 as compared to P2. As a result, improvements in color and other physical properties were observed for the polymers, not only during processing, but also after treatment with gamma radiation.