Poly(ethylene glycol)-block-poly(butyl acrylate). II. Characterization and properties

Poly(ethylene glycol)-block-poly(butyl acrylate) synthesized by radical polymerization in a one-step procedure were characterized by gel permeation chromatography, infrared, IH-NMR spectroscopy, and differential scanning calorimetry (DSC). The crystalline property, emulsifying property, and phase transfer catalytic effect in the Williamson reaction were studied. It was found that the crystallinity of the copolymer increased with an increase in both the content and molecular weight of poly( ethylene oxide) (PEO) sequences. DSC curves showed two distinct crystallization temperature due to the heterogeneous nucleation and homogeneous nucleation crystallization. The casting solvent significantly affected the morphology and crystallinity of the solvent cast films. Both the emulsifying volume and the phase transfer catalytic efficiency in the Williamson reaction increased with the amount and PEO content of the block copolymers used, but decreased with an increase in the molecular weight of PEO sequences. (C) 1998 John Wiley & Sons, Inc.

Miscibility and crystallization of poly(beta-hydroxybutyrate)/poly(vinyl acetate-co-vinyl alcohol) blends

Poly(vinyl acetate-co-vinyl alcohol) copolymers (P(VAc-co-VA)) were synthesized by hydrolysis-alcoholysis of PVAc. The miscibility, crystallization, and morphology of poly(P-hydroxybutyrate) (PHB) and P(VAc-co-VA) blends were studied by differential scanning calorimetry, optical microscopy (OM), and SAXS. It is found that the P(VAc-co-VA)s with vinyl alcohol content of 9, 15, and 22 mol % will form a miscible phase with the amorphous part of PHB in the solution-cast samples. The melting-quenched samples of PHB/P(VAc-co-VA) blends with different vinyl alcohol content show different phase behavior. PHB and P(VAc-co-VA9) with low vinyl alcohol content (9% mel) will form a miscible blend in the melt state. PHB and P(VAc-co-VA15) with 15 mol % vinyl alcohol will not form miscible blends while PHB/P(VAc-co-VA15) blend with 20/80 composition will form a partially miscible blend in the melt state. PHB and P(VAc-co-VA22) with 22 mol % vinyl alcohol are not miscible in the whole composition range. The single glass transition temperature of the blends within the whole composition range suggests that PHB and P(VAc-co-VA9) are totally miscible in the melt. The crystallization kinetics was studied from the whole crystallization and spherulite growth for the miscible blends. The equilibrium melting point of PHB in the PHB/P(VAc-co-VA9) blends, which was obtained from DSC results using the Hoffman-Weeks equation, decreases with the increase in P(VAc-co-VA9) content. The negative value of the interaction parameter determined from the equilibrium melting point depression supports the miscibility between the components. The kinetics of spherulitic crystallization of PHB in the blends was analyzed according to nucleation theory in the temperature range studied in this work. The best fit of the data to the kinetic theory is obtained by employing WLF parameters and the equilibrium melting points obtained by DSC. The addition of P(VAc-co-VA) did not affect the crystalline structure of PHB, as shown by the WAXD results. The long periods of blends obtained from SAXS increase with the increase in P(VAc-co-VA) content. It indicates that the amorphous P(VAc-co-VA) was rejected to interlamellar phase corporating with the amorphous part of PHB.

Efficient green electroluminescent cells using a poly(p-phenylene vinylene) multiblock copolymer sandwiched between carrier-transporting layers

With a newly synthesized poly(p-phenylene vinylene) (PPV) multiblock copolymer used in a triple-layer structure, efficient green light-emitting diodes with low driving voltage have been fabricated. The devices are turned on at 2.5 V, the brightness at 5 V is above 100 cd/m(2) and at 7 V is about 1650 cd/m(2), with an external quantum efficiency of about 1%. (C) 1998 Elsevier Science S.A. All rights reserved.

Physical aging and crystallization of amorphous poly(aryl ether ether ketone ketone)

Physical aging of poly(aryl ether ether ketone ketone) (PEEKK) was investigated. Heat flow responses were measured after annealing the amorphous samples that were obtained by quenching the melt into an ice-water bath at just below the glass transition temperature. Isothermal cold crystallization of the aged samples was carried out. The Avrami equation was used to determine the kinetic parameters, and the Avrami constant it is about 2. An Arrhenius form was used to evaluate the relaxation activation energy of physical aging and the transport activation energy of isothermal crystallization. The activation energy of physical aging was similar in magnitude to that observed for the temperature dependence of crystallization under conditions of transportation control. Results obtained were interpreted as purely kinetic effects associated with the glass formation process. (C) 1998 John Wiley & Sons, Inc.

Investigation of oxygen- and hydrogen peroxide-reduction on platinum particles dispersed on poly(o-phenylenediamine) film modified glassy carbon electrodes

Composite membrane modified electrodes were prepared by electrochemical deposition of platinum particles in a poly(o-phenylenediamine) (PPD) him coated on glassy carbon (GC) electrodes. The modified electrodes showed high catalytic activity towards the reduction of oxygen and hydrogen peroxide. A four-electron transfer process predominated the reduction process. The pH dependence and the stability of the electrodes were also studied.

The rheological and extrusion behaviour of blends based on phenolphthalein poly(ether-ether-sulfone) and thermotropic liquid crystalline polymer

A novel engineering thermoplastic, phenolphthalein poly (ether-ether-sulfone) (PES-C) was blended with a commercial thermotropic liquid crystalline polymer(TLCP), Vectra A950, up to 30 weight percent of TLCP. A rheometrics dynamic spectrometer (RDS-I) and a CEAST capillary rheometer, a rheoscope 1000 were employed to investigate the melt rheology and extrusion behaviour at both the low and high shearing rates. The morphologies of the blends under different shearing were observed with a scanning electron microscope(SEM) and correlated to the observed rheology. The principal normal stress differences measured with cone-and-plate geometry give a temperature-independent correlation for both blend and PES-C when they are plotted against shear stress. But the extrudate swell of the blends showed a strong temperature dependence at each shear stress. The concentration dependence of extrudate swell shows a contrary behaviour to that of the inorganic filled system. A reasonable hypothesis based on the relaxation and disorientation of TLCP during flowing in the capillary and exiting was given to explain it. The melt fracture was checked after extrusion from capillary and was discussed.

Synthesis and characterization of poly(amide imide)s containing cyclohexylidene moieties with bulky substituents

Novel poly(amide imide)s (PAI) containing alkyl-substituted cyclohexylidene moieties were synthesized by conventional polycondensation of trimellitic anhydride chloride with novel aromatic diamines followed by chemical imidization using acetic anhydride and pyridine. The inherent viscosities of the resulting PAIs are relatively high and range from 71 to 112 mt g(-1). The prepared PAIs show excellent thermal stability and good solubility. The glass transition temperatures (T-g) measured by DSC are observed in the range of 312-342 degrees C. Furthermore, all the polymers are readily soluble in less hygroscopic organic solvents like cyclohexanone, gamma-butyrolactone as well as aprotic polar solvents.

A study of the effect of shell content on the mechanical properties of polycarbonate/poly(butyl acrylate)-cs-poly(methyl methacrylate) blends

The toughening effect of the shell content of a core-shell latex polymer poly(butyl acrylate) (PBA)-cs-poly(methyl methacrylate) (PMMA) on its blends with polycarbonate (PC) was studied. The changes of mechanical properties, morphology, and compatibility of the blends of PC/PBA-cs-PMMA with the change of the shell thickness of PBA-cs-PMMA were investigated. It is interesting to notice that mechanical properties of the blends are very sensitive to the shell thickness (i.e., shell content), and that there is a possibility to adjust the impact and tensile properties of the blend by selecting a PBA-cs-PMMA with a proper core/shell ratio. Hence, a modified PC material with balanced mechanical properties may be prepared.

Crystallization and melting behavior of nylon 66 poly(ether imide) blends

Isothermal crystallization and melting behavior of nylon 66 and its blends with poly(ether imide) (PEI) were investigated by differential scanning calorimetry. Crystallization kinetics such as overall rate constant Z and index n were calculated according to Avrami approach. Crystallization in the blend was retarded with respect to that of pure nylon 66 by incorporation of PEI with high glass transition temperature (T-g). The lowest growth rate of the spherulites was observed in the blends containing 10 and 15 wt% fraction of PEI. A transition temperature where positively birefringent spherulites disappear and negative birefringent spherulites develop was measured by thermal analysis. The transition temperature increased with content of PEI in the blends. A suitable range of isothermally crystallization temperatures, 238.5-246 degrees C, is suggested For determining the equilibrium melting points by means of Hoffman-Weeks approach.

Miscibility and specific interactions in poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) and poly(P-vinylphenol) blends

The blends of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) (P(HB-co-HV)/poly(p-vinylphenol)(PVPh) were investigated by differential scanning calorimetry (DSC), Fourier transform IR (FT-IR) spectroscopy and high-resolution solid-state C-13 NMR techniques. Single glass transition temperatures existing in the whole composition range indicates that these blends are miscible. The presence of hydrogen bonding between the hydroxyl of PVPh and carbonyl of P(HB-co-HV), shown by FT-IR spectra, is the origin of the miscibility. Furthermore, results obtained by high-resolution solid-state C-13 NMR give more information about the structure of the blends. (C) 1998 Elsevier Science Ltd. All rights reserved.

The synthesis and characterization of the novel poly(aryl ether ketone)s with liquid crystallinity

The novel poly(aryl ether ketone)s with liquid crystallinity were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and substituted hydroquinone with 4,4'-difluorobenzophenone and their thermotropic liquid crystalline properties were characterized by DSC, PLM and WAXD, The copolymers containing 70% biphenol formed nematic phase while the copolymer containing 50% biphenol exhibited smectic texture, The banded textures were formed after shearing the sample in the nematic liquid crystalline state. The identification of the structures in each mesogenic phase has been carried out by combining WAXD with PLM and DSC.

Influence of annealing on structure of poly(aryl ether ether ketone ketone) revealed by SAXS

Structural studies of poly(aryl ether ether ketone ketone) (PEEKK) using small-angle X-ray scattering and one-dimensional electron density correlation function methods revealed that its aggregated state structure was significantly influenced by the annealing temperature. The long period L, the average thickness of the lamellae d, the electron density difference between the crystalline and amorphous regions eta(c) - eta(a), and the invariant Q increased with increasing annealing temperature, but it was opposite to the case of the specific inner surfaces O-s. A transition zone existed between the traditional "two phases" with a dimension about 0.5 nm for semicrystalline PEEKK. (C) 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1829-1835, 1998.

Sodium sulfonate-functionalized poly(ether ether ketone)s

A new monomer, sodium 5,5'-carbonylbis(2-fluorobenzenesulfonate) (1), was synthesized by sulfonation of 4,4'-difluorobenzophenone (2) with fuming sulfuric acid. Poly(ether ether ketone)s containing sodium sulfonate groups were synthesized directly via aromatic nucleophilic substitution from the sodium sulfonate-functionalized monomer 1 and Bisphenol A (3) in the presence of potassium carbonate in dimethyl sulfoxide. The polycondensation proceeds without any side reactions. The differential scanning calorimetry measurement indicated that the polymers are amorphous and the glass transition temperatures increase with the content of sodium sulfonate groups in the polymer chain. The degree of substitution with sodium sulfonate groups has strong influence on their thermal stability and solubility.

Preparation and characterization of phenoxy resin/poly(4-vinylpyridine) interpolymer complexes

The compositions and structures of interpolymer complexes formed by mixing phenoxy resin (PHEB) and poly (4-vinylpyridine) (P4VPy) in chloroform have been studied by means of elemental analysis, DSC, FTIR, UV and XPS, In the meantime, the corresponding blends prepared have been characterized and compared. The results show that compositions of the complexes were identical with the ratio of equimolar interactive units. All blends were miscible and their compositions were related to the feed ratios. Based on the experimental results, process of formation of the complex is depicted.