Synthesis and optical properties of a poly(p‐phenylenevinylene) derivative and polyfluorenes with bipolar groups along the main chain

A poly(p‐phenylenevinylene) derivative (PPV–TPA)] and a series of statistical copolyfluorenes (PF–TPA)] containing oxadiazole and triphenylamine segments along the main chain were synthesized by the Heck reaction and nickel‐mediated coupling, respectively. The PF–TPA copolyfluorenes with relatively low contents of oxadiazole and triphenylamine units were readily soluble in common organic solvents, whereas the other copolyfluorenes displayed lower solubility. PPV–TPA showed excellent solubility in solvents such as tetrahydrofuran (THF), dichloromethane, chloroform, and toluene. Thin films of the polymers absorbed light in the range of 375–396 nm and had optical band gaps of 2.76–2.98 eV. They emitted blue‐green light with a maximum at 414–522 nm. The fluorescence quantum yields in THF solutions were 0.08–0.53. The copolyfluorene PF–TPA thin films with high contents of oxadiazole and triphenylamine moieties emitted pure blue light that remained stable even after annealing at 150 °C for 4 h in air. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3556–3566, 2006     

Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006     

Synthesis and characterization of poly(arylene ether)s containing 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one or 6‐(4‐hydroxyphenyl)pyridazine moieties

A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (T_g's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The T_g's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed T_g's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐T_g polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006     

Novel blue‐greenish electroluminescent poly(fluorenevinylene‐alt‐dibenzothiophenevinylene)s and their model compounds

Poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐2,8‐vinylene) (PS) and poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐5,5‐dioxide‐2,8‐ vinylene) (PSO) as well as corresponding model compounds were synthesized by Heck coupling. Both the polymers and model compounds were readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane, chloroform, and toluene. The polymers showed a decomposition temperature at ～430 °C and a char yield of about 65% at 800 °C in N₂. The glass‐transition temperatures of the polymers were almost identical (75–77 °C) and higher than those of the model compounds (26–45 °C). All samples absorbed around 390 nm, and their optical band gaps were 2.69–2.85 eV. They behaved as blue‐greenish light emitting materials in both solutions and thin films, with photoluminescence emission maxima at 450–483 nm and photoluminescence quantum yields of 0.52–0.72 in solution. Organic light‐emitting diodes with an indium tin oxide/poly(ethylene dioxythiophene):poly(styrene sulfonic acid)/polymer/Mg:Ag/Ag configuration with polymers PS and PSO as emitting layers showed green electroluminescence with maxima at 530 and 540 nm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6790–6800, 2006     

Polymer electrolyte membranes for the direct methanol fuel cell: A review

The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006     

Probing the use of small‐angle light scattering for characterizing structure of titanium dioxide/low‐density polyethylene nanocomposites

Small‐angle light scattering (SALS) measurements were used to study the structure of titanium dioxide (TiO₂)/low‐density polyethylene (LDPE) nanocomposites. The results showed that the scattering from LDPE crystalline structures and the scattering from TiO₂ nanoparticles can be resolved and separated. It is shown that the independent effects of crystallization conditions and the presence of nanoparticle aggregates on the spherulitic structure of the LDPE matrix can be determined by analyzing the scattering patterns using the methods proposed. From the SALS results, we conclude that the nanoparticle surface chemistry affects both nucleation of spherulites and their structure particularly under rapid cooling conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1084–1095, 2006     

Acrylic acid level and adhesive performance and peel master‐curves of acrylic pressure‐sensitive adhesives

Three series of pressure‐sensitive adhesives were prepared with constant glass‐transition temperature, using emulsion polymerization. The monomers chosen were butyl acrylate, 2‐ethylhexyl acrylate (EHA), methyl methacrylate (MMA), and acrylic acid (AA). Within each polymer series, the proportion of AA monomer was held constant for each polymer preparation but acrylic ester monomer levels were varied. Adhesion performance was assessed by measurement of loop tack, static shear resistance, and through the construction of peel master‐curves. Peel master‐curves were generated through peel tests conducted over a range of temperatures and peel rates and through application of the time–temperature superposition principle. Bulk effects dominated by polymer zero shear viscosity change as AA and EHA levels were varied were attributed to the observed effect on static shear resistance and the horizontal displacements of peel master‐curves. Static shear resistance was found to strongly correlate with log(a_C), a parameter introduced to horizontally shift peel master‐curves to form a superposed, “super master‐curve”. An interfacial interaction was proposed to account for deviations observed when loop tack was correlated with log(a_C). Surface rearrangements via hydrogen bonding with the test substrate were suggested as responsible for the interfacial interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1237–1252, 2006     

Rheology,morphology, and estimation of the interfacial tension of binary blends based on low‐density polyethylene/poly(trimethylene terephthalate) and high‐density polyethylene/poly(trimethylene terephthalate) [retracted article]

It has come to our attention that this article, “Rheology, Morphology, and Estimation of the Interfacial Tension of Binary Blends Based on Low‐Density Polyethylene/Poly(trimethylene terephthalate) and High‐Density Polyethylene/Poly(trimethylene terephthalate)” by A. A. Shokri and S. E. Zamani was previously published under the title, “Rheology, Morphology and Estimation of Interfacial Tension of LDPE/EVA and HDPE/EVA Blends” by H. A. Khonakdar, S. H. Jafari, A. Yavari, A. Asadinezhad, U. Wagenknecht, in Polymer Bulletin 54, 75–84 (2005), . We have retracted the article, and offer our apologies to the authors of the original paper.     

Indirect fluorometric determination of diclofenac sodium.

A simple and easy method of analysis for diclofenac sodium is reported. A spectrofluorometric method for the microdetermination of diclofenac sodium has been developed through its reaction with cerium(IV) in an acidic solution and measurement of the fluorescence of the Ce(III) ions produced. Under the optimum experimental conditions for the oxidation reaction, 1.0 M H2SO4 with 90 min of heating time (100 degrees C), the range of application is 124.3-600 ng mL(-1) and the limit of detection is 72.7 ng mL(-1). The proposed method was applied to the determination of diclofenac sodium in pharmaceutical tablets. The results of the analysis show a good agreement with those obtained by the official USP 27 HPLC method.     

Ferromagnetic material CdGeP2:Mn for spintronics

Solid solutions Cd_1?x Mn_xGeP₂ (x=0?0.19) have been synthesized and identified. In these solutions, the unit cell parameters decrease with an increase in the manganese content. The solid solution Cd_0.81Mn_0.19GeP₂ is a ferromagnet with the Curie temperature T _C ≈ 311 K. The paramagnetic moment of Mn²⁺ ions equal to 5.8 μ_B, as well as the spontaneous magnetization constituting 76% of the total magnetization of a crystal, has been determined with the use of the Langevin function. The origin of ferromagnetism in CdGeP₂:Mn is exchange mediated by charge carriers (holes). These holes are caused by cationic defects in the structure of chalcopyrite.