Grafting of maleic anhydride onto linear polyethylene: A Monte Carlo study

Monte Carlo simulation was used to study the graft of maleic anhydride (MAH) onto linear polyethylene (PE-g-MAH) initiated by dicumyl peroxide (DCP). Simulation results revealed that major MAH monomers attached onto PE chains as branched graft at higher MAH content. However, at extremely low MAH content, the fraction of bridged graft was very close to that of branched graft. This conclusion was somewhat different from the conventional viewpoint, namely, the fraction of bridged graft was always much lower than that of branched graft under any condition. Moreover, the results indicated that the grafting degree increased almost linearly to MAH and DCP concentrations. On the other hand, it was found that the amount of grafted MAH dropped sharply with increasing the length of grafted MAH, indicating that MAH monomers were mainly attached onto the PE chain as single MAH groups or very short oligomers. With respect to the crosslink of PE, the results showed that the fraction of PE-(MAH)(n)-PE crosslink structure increased continuously, and hence the fraction of PE-PE crosslink decreased with increasing MAH concentration.

White electrolumineseence from a single-polymer system with simultaneous two-color emission: Polyfluorene as the blue host and a 2,1,3-benzothiadiazole derivative as the orange dopant on the main chain

New single-polymer electroluminescent systems containing two individual emission species - polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain - have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue(lambda(max) = 421 nm/445 nm) and orange emission (lambda(max) = 564 nm)from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m(-2), luminance efficiency of 7.30 cd A(-1), and power efficiency of 3.34 lm W-1 can be obtained.

Reversible B/Z-DNA transition under the low salt condition and non-B-form polydApolydT selectivity by a cubane-like europium-L-aspartic acid complex

We report here that a cubane-like europium-L-aspartic acid complex at physiological pH can discriminate between DNA structures as judged by the comparison of thermal denaturation, binding stoichiometry, temperature-dependent fluorescence enhancement, and circular dichroism and gel electrophoresis studies. This complex can selectively stabilize non-B-form DNA polydApolydT but destabilize polydGdCpolydGdC and polydAdTpolydAdT. Further studies show that this complex can convert B-form polydGdCpolydGdC to Z-form under the low salt condition at physiological temperature 37 degrees C, and the transition is reversible, similar to RNA polymerase, which turns unwound DNA into Z-DNA and converts it back to B-DNA after transcription. The potential uses of a left-handed helix-selective probe in biology are obvious. Z-DNA is a transient structure and does not exist as a stable feature of the double helix. Therefore, probing this transient structure with a metal-amino acid complex under the low salt condition at physiological temperature would provide insights into their transitions in vivo and are of great interest.

Effects of chain flexibility on polymer conformation in dilute solution studied by lattice Monte Carlo simulation

Effects of chain flexibility on the conformation of homopolymers in good solvents have been investigated by Monte Carlo simulation. Bond angle constraint coupled with persistence length of polymer chains has been introduced in the modified eight-site bond fluctuation simulation model. The study about the effects of chain flexibility on polymer sizes reveals that the orientation of polymer chains under confinement is driven by the loss of conformation entropy. The conformation of polymer chains undergoing a gradual change from spherical iso-diametric ellipsoid to rodlike iso-diametric ellipsoid with the decrease of polymer chain flexibility in a wide region has been clearly illustrated from several aspects. Furthermore, a comparison of the freely jointed chain (FJC) model and the wormlike chain (WLC) model has also been made to describe the polymer sizes in terms of chain flexibility and quasi-quantitative boundary toward the suitability of the models.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

Phenylene vinylene-based electroluminescent polymers with electron transport block in the main chain

We report a new route for the design of soluble phenylene vinylene (PV) based electroluminescent polymers bearing electron-deficient oxadizole (OXD) and triazole (TZ) moieties in the main chains with the aryloxy linkage. Both series of the PV-based polymers were prepared by Wittig reaction. By properly adjusting the OXD and/or TZ content through copolymerization, we can achieve an enhanced balance of hole- and electron injections, such that the device efficiency is significantly improved. Light-emitting diodes fabricated from P1, P2, P3, P4, P5, P6, and P7 with the configuration of Indium-Tin Oxide (ITO)/Poly (styrene sulfonic acid) doped poly (ethylenedioxythiophene) (PEDOT)/polymer/Ca/Al, emit bright green light with the maximum peak around 500 nm. For the device using the optimal polymer (P4) as emitting layer, a maximum brightness of 1300 cd/m(2) at 20 V and a maximum luminance efficiency of 0.325 cd/A can be obtained.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Column chromatographic purification free synthesis of long-chain monodisperse oligo(1,4-phenyleneethynylene)s: towards large-scale automatic synthesis of molecular wires

A facile, mild and rapid solid phase synthetic route free of column chromatographic purification to the synthesis of soluble monodisperse long-chain oligo(1,4-phenyleneethynylene)s is presented.

Synthesis, crystal structure and magnetic properties of a chain coordination polymer {[Cu4L2(H2O)] center dot H2O}(n)

A chain coordination polymer with the chemical formula {[Cu4L2(H2O)] (.) H2O)(n), has been synthesized by the assembly reaction of K(2)CuL(.)1.5H(2)O and Cu(OAC)(2)(H2O)-H-. with a 1:1 mole ratio in methanol., where H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl I imino)methyl] benzoic acid, OAC(-) = CH3COO-. The crystal structure was determined by single-crystal X-ray diffraction analysis, the compound has chain molecular structure formed by dissymmetrical tetranuclear units. The magnetic measurements showed that Cu-Cu of the complex exhibit antiferromagnetic interactions, and satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a binuclear system, and further using molecular field approximation to deal with magnetic exchange interactions between binuclear systems.

Effect of chain-length dependence of interaction parameter on spinodals for polydisperse polymer blends

The chain-length dependence of the Flory-Huggins (FH) interaction parameter is introduced into the FH lattice theory for polydisperse polymer-blend systems. The spinodals are calculated for the model polymer blends with different chain lengths and distributions. It is found that all the related variables r(n), r(w), r(z), and chain-length distribution, have effects on the spinodals for polydisperse polymer blends.

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

The effects of the chain structure and the intramolecular interaction energy of an A/B copolymer on the miscibility of the binary blends of the copolymer and homopolymer C have been studied by means of a Monte Carlo simulation. In the system, the interactions between segments A, B and C are more repulsive than those between themselves. In order to study the effect of the chain structure of the A/B copolymer on the miscibility, the alternating, random and block copolymers were introduced in the simulations, respectively. The simulation results show that the miscibility of the binary blends strongly depends on the intramolecular interaction energy ((ε) over bar (AB)) between segments A and B within the A/B copolymers. The higher the repulsive interaction energy, the more miscible the A/B copolymer and homopolymer C are. For the diblock copolymer/homopolymer blends, they tend to form micro phase domains. However, the phase domains become so small that the blend can be considered as a homogeneous phase for the alternating copolymer/ homopolymer blends. Furthermore, the investigation of the average end-to-end distance ((h) over bar) in different systems indicates that the copolymer chains tend to coil with the decrease Of (ε) over bar (AB) whereas the (h) over bar of the homopolymer chains depends on the chain structure of the copolymers.

Shear induced molecular alignments of a side-chain liquid crystalline polyacetylene containing biphenyl mesogens

Mesomorphic properties of a side chain liquid crystalline polyacetylene, poly(11-{[(4'-heptyloxy-4-biphenylyl)carbonyl]oxy}-1-undecyne) (PA9EO7), are investigated using polarized optical microscope, X-ray diffraction, and transmission electron microscope. Polymer PA9EO7 forms enantiotropic smectic A and smectic B phases. It also exhibits an additional high order smectic phase, a sandwich structure consisting of different molecular packing of biphenyl mesogenic moieties from that of alkyl spacers and terminals, when it is prepared from its toluene solution. Shearing the polymer film at its smectic A phase generates banded texture with the alignment of the backbones parallel to the direction of shear force. While at its high order smectic phase, the mesogen pendants of the polymer are arranged parallel to the direction of shear. The different mesomorphic behaviors arise from different molecular alignments influenced by the fluidity.

Nanometer scale mechanical study on well defined nanostructured chain aggregation of polyethylene

Two kinds of polyethylene chain aggregation with chain axis perpendicular and parallel to the supported substrate were designed and successfully obtained from melt under an electric field and by melt-drawn method

An unusual organic-inorganic chain-like hybrid complex [(CuCl)(2)(o-phen)](infinity) (o-phen=o-phenanthroline)

A novel organic-inorganic hybrid complex [(CuCl)(2) (o-phen)](infinity) 1 (o-phen = o-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analyses, XPS spectrum, TG analysis, and single-crystal X-ray diffraction. Compound I crystallizes in the monoclinic system, space group P2(1)/n, a = 3.7285(7) Angstrom, b = 19.603(4) Angstrom, c = 16.757(3) Angstrom, beta = 95.83(3)degrees, V = 1218.4(4) Angstrom(3), Z = 4, lambda(MoKalpha) = 0.71073 Angstrom (R(F) = 0.0643 for 2559 reflections). Data were collected on an R-axis RAPID diffractometer at 293 K in the range of 1.60 < θ < 27.48degrees. The title compound exhibits a one-dimensional chain-like scaffolding constructed by the unusual [Cu3Cl3] hexagon motifs by, sharing opposite edges. Only Cu(1) sites of the [Cu3Cl3] hexagon are coordinated with N donors of o-phen groups. Furthermore, the three-dimensional supermolecular architecture is formed by C-H...Cl hydrogen bonds between o-phen groups and CuCl chains.