Electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40), in polyethylene glycol

The electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40) (abbreviated as PMo12-Co), have been studied in poly(ethylene glycol) for four different molecular weights (PEG, average MW 400, 600, 1000, and 2000 g mol(-1)) and containing LiClO4 (O/Li=100/1) supporting electrolyte. The diffusion coefficients of the PMo12-Co nanoparticles were determined using a microelectrode by chronoamperometry for PEG of different molecular weights that were used to describe the diffusion behavior of PMo12-Co nanoparticles in different phase states. Moreover, the conductivity of the composite system increases upon addition of PMo12-Co nanoparticles, which was measured by an a.c. impedance technique. FT-IR spectra and DSC were used to follow the interactions of PEG-LiClO4-PMo12-Co, and well described the reason that the PMo12-Co nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.

What has brought on the effects of number-average molecular weight on the spinodals in polymer mixtures?

On the basis of the thermodynamics of Gibbs, the spinodal for the quasibinary system was derived in the framework of the Sanchez-Lacombe lattice fluid theory. All of the spinodals were calculated based on a model polydisperse polymer mixture, where each polymer contains three different molecular weight subcomponents. According to our calculations, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights, whereas that of the z-average molecular weight is invisible. Moreover, the extreme of the spinodal decreases when the polydispersity index (eta = (M) over bar (w)/(M) over bar (n)) of the polymer increases. The effect of polydispersity on the spinodal decreases when the molecular weight gets larger and can be negligible at a certain large molecular weight. It is well-known that the influence of polydispersity on the phase equilibrium (coexisting curve, cloud point curves) is much more pronounced than on the spinodal. The effect of M, on the spinodal is discussed as it results from the infuluence of composition temperatures, molecular weight, and the latter's distribution on free volume. An approximate expression, which is in the assumptions of v* v(1)* = v(2)* and 1/r --> 0 for both of the polymers, was also derived for simplification. It can be used in high molecular weight, although it failed to make visible the effect of number-average molecular weight on the spinodal.

Polyimides from isomeric biphenyltetracarboxylic dianhydrides and the effects of chemical structure on solubility

A series of homopolyimides and copolyimides was synthesized by the solution condensation of biphenyltetracarboxylic dianhydride (BPDA) isomers and various diamines followed by chemical imidization. These polyimides had intermediate to high molecular weights with inherent viscosities of 0.34-1.01 dL/g for homopolyimides and 0.48-1.02 dL/g for copolyimides. Thermogravimetric analysis indicated that the aromatic polyimides were stable up to 500degreesC, and the 5% weight loss temperatures were recorded in the range of 506-597degreesC in an air atmosphere and in the range of 517-601degreesC in a nitrogen atmosphere, depending on the diamines used. The glass transition temperatures of aromatic homopolyimides were above 271degreesC, while the glass transition temperatures of the copolyimides increased with an increase in the 2, 2', 3, 3'-BPDA-component. The effects of the chemical structure of the polymer chain on the solubility were investigated. It was found that the solubility of BPDA-based polyimides could be improved by the introduction of flexible units, nonlinear and non-coplanar units, and copolymerization. The polyimides with nonlinear and non-coplanar units derived from 2, 2', 3, 3'-BPDA appeared to have prominently enhanced solubility in polar aprotic solvents and polychlorocarbons when compared with the homopolyimide derived from 3, 3', 4, 4'-BPDA.

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.

Effects of pressure and molecular weight on the miscibility of polystyrene and cyclohexane

With the aid of Sanchez-Lacombe lattice fluid theory (SLLFT), the phase diagrams were calculated for the system cyclohexane (CH)/polystyrene (PS) with different molecular weights at different pressures. The experimental data is in reasonable agreement with SLLFT calculations. The total Gibbs interaction energy, g*(12) for different molecular weights PS at different pressures was expressed, by means of a universal relationship, as g(12)* =f(12)* + (P - P-0) nu*(12) demixing curves were then calculated at fixed (near critical) compositions of CH and PS systems for different molecular weights. The pressures of optimum miscibility obtained from the Gibbs interaction energy are close to those measured by Wolf and coworkers. Furthermore, a reasonable explanation was given for the earlier observation of Saeki et al., i.e., the phase separation temperatures of the present system increase with the increase of pressure for the low molecular weight of the polymer whereas they decrease for the higher molecular weight polymers. The effects of molecular weight, pressure, temperature and composition on the Flory Huggins interaction parameter can be described by a general equation resulting from fitting the interaction parameters by means of Sanchez-Lacombe lattice fluid theory.

Theoretical calculation of Flory-Huggins and scattering interaction parameters by means of the lattice fluid theory for PVME/PSD blends

By fitting the spinodals of poly(vinyl methyl ether)/deuterated polystyrene (PVME/PSD) systems, the adjustable parameters epsilon (12)* and delta epsilon* in the Sanchez-Balasz lattice fluid (SBLF) theory could be determined for different molecular weights. According to these parameters, Flory-Huggins and scattering interaction parameters were calculated for PVME/PSD with different molecular weights by means of the SELF theory. From our calculation, Flory-Huggins and scattering interaction parameters are both Linearly dependent on the reciprocal of the temperature, and almost linearly on the concentration of PSD. Compared with the scattering interaction parameters, the Flory-Huggins interaction parameters decreased more slowly with an increase in the concentration for all three series of blends.

Study of the conductivity and side chain mobility of a comb-like polymer electrolyte using the dynamic mechanical method

Using poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether (PEGME) with different molecular weights as side chains, three comb-like polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the polymer electrolytes possess two glass transitions: alpha -transition and beta -transition, and the temperature dependence of the ionic conductivity shows WLF (Williams-Landel-Ferry) behavior. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T-beta as reference temperature. The values of the WLF parameters (C-1 and C-2) were obtained and were found to be almost independent of the length of the PEGME side chain and the content of Li salt. By reference to T-0 = 50 degreesC. the relation between log tau (c) and c was found to be linear. The master curves are displaced progressively to higher frequencies as the molecular weight of the side chain is increased. The relation between log tau (n) and the molecular weight of the side chain is also linear. (C) 2001 Elsevier Science B.V. All rights reserved.

Studies on the structure and properties of thermotropic liquid crystalline poly(aryl ether ketone)s

Series of thermotropic liquid crystalline poly (aryl ether ketone) s were synthesized by mucleophilic substitution reactions of 4,4'-biphenol and substituted hydroquinone with different difluoromonomers, The relationship between structure and properties of the novel copolymers was investigated. For the copolymers with liquid crystalline properties, their melting transition temperatures show no great change with increase the content of the crystal-disrupting unit. The reason is that the crystal phase is directly transformed from the ordered liquid crystal phase. Side-groups have important effect on mesophase stability, The temperature range of mesophase stability for the chloro-polymers is smaller than those of other series of copolymers (P-phenyl, t-butyl, methoxy, 3-trifluoromethylbenzene). This behavior indicates that the effect of geometric repulsive factor on the thermodynamic stability of the mesophase is much larger than that of the polarizability attractive factor. Different ordered liquid crystal phases are observed in the polymers with different molecular weights. At low molecular weight, highly ordered smectic liquid crystal phases form. With increasing the molecular weight, the ordered degree of the liquid crystals decreases, and only the nematic liquid crystal phase is observed in the polymer with higher molecular weight.

Polymerization of acrylonitrile with organolanthanides as single-component catalysts

Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) were used as a single-component catalyst for the polymerization of acrylonitrile (AN) respectively. The regularity of polymerization of AN and stereoregularity of polyacrylonitrile (PAN) were also studied in both cases. Both catalysts can produce PAN with molecular weight from 10,000 to 30,000. In addition, the catalytic activity and molecular weights were increased by the addition of PhONa.

Mixing enthalpy and phase behavior of PEO/PVAc blends

Phase behaviors and heats of mixing of the miscible blends of poly(ethylene oxide) (PEO) and poly(vinyl acetate) (PVAc) with different molecular weights were investigated by DSC. A method proposed by Natasohn and Ebert et al. was adopted to estimate the binodal temperatures and the enthalpies of mixing from onset temperatures and values of areas of a series of endothermic peaks (corresponding to heats of demixing), respectively, in their heating scanning thermograms obtained with different heating rates. Phase diagrams and heats of mixing of this blending system were also predicted by using Sanchez-Lacombe lattice fluid theory. A very good agreement was obtained for both. phase behaviors and heats of mixing obtained with two different methods.

Synthesis of aromatic polyimides in DMAc containing large amount of water and the properties thereof

A series of polyamic acids were prepared in N,N-dimethylactamide (DMAc) containing large amount of water, some of which contain the amount of water up to 25%. Their inherent viscosities decreased with the increase of water in DMAc, depending on the electronic properties of dianhydride and reaction condition. The molecular weights and mechanical properties of the polyimides thermally imidized from the polyamic acids were almost independent on the water content in solvent. The decomposition-resynthesis of polyamic acids during the curing was also investigated.

Matrixassisted laser desorption/ionization mass spectral study of saccharides

Matrixassisted laser desorption/ionization (MALDI) mass spectra of saccharides with three common matrixes were studied here. It is shown that Na+ and K+ play important roles in the determination of oligasaccharide molecule weight and the molecular weights (MW) of glucans(dextran) with MW more than 10 000 is determined successfully with the help of column chromatography, By comparing the effects of three matrixes in saccharide analysis and comparing positive-ion and negative-ion matrixassisted laser desorption/ionization mass spectra of oligo- and polysaccharides, the most suitable matrix for saccharide analysis, 2,5-dihydroxylbezonic acid (DHB), is selected and the ion formation processes of saccharides under matrix-assisted laser adsorption/ionization condition are clarified.

Studies on water-swellable elastomers .2. Thermal properties and crystalline behavior of amphiphilic graft copolymers with poly(ethylene glycol) side chains

The thermal properties and crystalline structure of the amphiphilic graft copolymers CR-g-PEG600, CR-g-PEG2000, and CR-g-PEG6000 using chloroprene rubber (CR) as the hydrophobic backbone and poly(ethylene glycol) (PEG) with different molecular weights as the hydrophilic side chains were studied by DSC and WAXD. The results showed that a distinct phase-separated structure existed in CR-g-PEGs because of the incompatibility between the backbone segments and the side-chain segments. For all the polymers studied, T-m2, which is the melting point of PEG crystalline domains in CR-g-PEG, decreased compared to that of the corresponding pure PEG and varied little with PEG content. For CR-g-PEG600 and CR-g-PEG2000, T-m1, which is the melting point of the CR crystalline domains, increased with increasing PEG content when the PEG content was not high enough, and at constant PEG content, the longer were the PEG side chains the higher was the T-m1. The crystallite size L-011 of CR in CR-g-PEGs increased compared to that of the pure CR and decreased with increasing PEG content. (C) 1997 John Wiley & Sons, Inc.

Laser light scattering of the molecular weight distribution of unfractionated phenolphthalein poly(aryl ether sulfone)

Two unfractionated samples of phenolphthalein poly( aryl ether sulfone) (PES-C) were characterized in CHCl3 at 25 degrees C by applying a recently developed laser light-scattering (LLS) procedure. The Laplace inversion of precisely measured intensity-intensity time correlation function lead us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). A combination of static and dynamic LLS results enabled us to determine D = (2.69 x 10(-4))M(-0.553), which agrees with the calibration of D = (2.45 x 10(-4))M(-0.55) previously established by a set of narrowly distributed PES-C samples. Using this newly obtained scaling between D and M, we were able to convert G(D) into a differential weight distribution f(w)(M) for the two PES-C samples. The weight-average molecular weights calculated from f(w)(M) are comparable to that obtained directly from static LLS. Our results showed that using two broadly distributed samples instead of a set of narrowly distributed samples have provided not only similar final results, but also a more practical method for the PES-C characterization. (C) 1997 John Wiley & Sons, Inc.

Crystallization behaviour of poly(ether ether ketone)/poly(ether sulfone) block copolymer

The crystallization and melting behaviours of a multiblock copolymer comprising poly(ether ether ketone) (PEEK) and poly(ether sulfone) (PES) blocks whose number average molecular weights <((M)over bar (n)'s)> were 10 000 and 2900, respectively, were studied. The effect of thermal history on crystallization was investigated by wide-angle X-ray diffraction measurement. A differential scanning calorimeter was used to detect the thermal transitions and to monitor the energy evolved during the isothermal crystallization process from the melt. The results suggest that the crystallization of the copolymer becomes more difficult as compared with that of pure PEEK. The equilibrium melting point of the copolymer was found to be 357 degrees C, about 30 degrees C lower than that of pure PEEK. During the isothermal crystallization, relative crystallinity increased with crystallization time, following an Avrami equation with exponent n approximate to 2. The fold surface free energy for the copolymer crystallized from the melt was calculated to be 73 erg cm(-2), about 24 erg cm(-2) higher than that of pure PEEK. Copyright (C) 1996 Elsevier Science Ltd.