Synthesis and characterization of hyperbranched aromatic poly(ether imide)s

The four AB(2) monomers, N-[3- or 4-bis(4-hydroxyphenyl)toluoyl]-4-chlorophthalimide and N-{3- or 4-[1,1-bis(4-hydroxyphenyl)]ethylphenyl}-4-chlorophthalimides, were prepared and used for synthesis of hyperbranched poly(ether imide)s bearing hydroxyl end groups. These hyperbranched poly(ether imide)s had moderate molecular weights with broad distributions and showed glass-transition temperatures (Tgs) between 177 and 230 degreesC. The thermogravimetric analytic measurement revealed the decomposition temperature at 5% weight-loss temperatures (T-d(5%)) ranging from 240 to 281 degreesC. Analysis using H-1 NMR spectroscopy revealed the four types of hyperbranched poly(ether imide)s to have similar degrees of branching (ca. 60%). These polymers were modified by acylation or nucleophilic substitution reaction at the hydroxyl end groups. The conversion effectiveness depended on the type of modification reaction, modifier, and reaction conditions. The thermal stability and solubility of hyperbranched poly(ether imide)s were improved by the modification of the end groups.

Reactive reinforcement of the interface of poly(ether sulfone)/poly(phenylene sulfide) polymer blend by PMR-POI

The effect of polymerization of monomer reactant-polyimide (POI) as the interfacial agent on the interface characteristics, morphology features, and crystallization of poly(ether sulfone)/poly(phenylene sulfide) (PES/PPS) blends were investigated using a scanning electron microscope, FTIR, WAXD, and XPS surface analysis. It was found that the interfacial adhesion was enhanced, the particle size of the dispersed phase was reduced, and the miscibility between PES and PPS was improved by the addition of POI. It was also found that POI was an effective nucleation agent of the crystallization for PPS.

Thermally crosslinkable poly(phenylene sulfide)/poly (ether sulfone)/polymerization of monomer reactant-polyimide blends

The effects of thermally crosslinkable polymerization of monomer reactant-polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature.

Influence of intermolecular entanglements on the glass transition and structural relaxation behaviors of macromolecules. 2. Polystyrene and phenolphthalein poly(ether sulfone)

The effect of entanglements on the glass transition and structural relaxation behaviors has been studied for polystyrene (PS) and phenolphthalein poly(ether sulfone) (PES-C) samples by fast evaporation of the solution of concentrations varying from above the overlapping concentration to far below it, and compared to the results we have studied previously in PC. It has been found that for all the polymers we have studied, in the concentrated solution region, the T-g of the samples obtained from solution are independent of the change of concentration and are very close to that of normal bulk samples, whereas in the dilute solution region the T-g of the samples decrease with the logarithm of decreasing concentration. The critical concentrations that divide the two distinct regions for the three polymers are 0.9% g/mL for PC, 0.1% g/mL for PS, and 1% g/mL for PES-C. The decrease of T-g of the samples is interpreted by the decrease of intermolecular entanglements as the isolation of polymer chains, and the entanglement of polymer chains restrained the mobility of the segments. The structural relaxation behavior of the polymers is also found to be different from that of normal bulk samples. The enthalpies of single-chain samples are lower than that of the bulk ones, which correspond to the lower glass transition temperature; the peaks are lower and broader, and the relaxed enthalpy is much lower as compared to that of bulk samples. In the three polymers we have studied, the influence of change of entanglements on both the decrease in glass transition temperature and relaxed enthalpy is the most significant for PS and the least for PES-C. It is indicated that the interactions in the flexible polymers are weak; thus, the restraint of the entanglements on the mobility of the segments plays a more important role in the flexible polymers, and the change of entanglement in the flexible polymers has a more significant influence on the physical properties.

Characterization and ionic conductivity of an amorphous comblike polymer - II: Based on ethylene maleic anhydride copolymer backbone with monoethyl ether of poly(ethylene glycol) of M-W=550 as side chain

Using a graft modification method, a comblike polymer host (CBPE550) was synthesized by reacting monomethyl ether of poly(ethylene glycol) (PEGMA) with ethylene-maleic anhydride copolymer (EMAC) and endcapping the residual carboxylic acid with methanol. The product was characterized by IR and elementary analysis. Result showed that the product was amorphous and semi-ester product is accord with reaction equation. There were two peaks in the plot of the ionic conductivity against Li salt concentration. The plot of log a against 1/(T - T-0) shows a dual VTF behavior when using the glass transition temperature of PEO of side chain as T beta. The comblike polymer is a white rubbery solid. It can be well-dissolved in acetone. (C) 1999 Elsevier Science Ltd. All rights reserved.

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.

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.

Impact behavior of phenolphthalein poly(ether sulfone) ultrahigh molecular weight polyethylene blends

This work presents the structure and impact properties of phenolphthalein poly(ether sulfone) blended with ultrahigh molecular weight polyethylene (PES-C/UHMWPE) at different compositions. The addition of UHMWPE can considerably improve the Charpy and Izod impact strength of the blends. The fracture surface is examined to demonstrate the toughening mechanics related to the modified PES-C resin. (C) 1998 John Wiley & Sons, Inc.

Mechanical and structural characteristics of phenolphthalein poly(ether sulfone) ultra-high molecular weight polyethylene blends

Mechanical and structural properties of blends of phenolphthalein poly(ether sulfone) (PBS-C) with ultra-high molecular weight polyethylene (UHMWPE) were investigated using tensile and bending testing, scanning electron microscopy and transition electron microscopy. The incorporation of minor amounts of UHMWPE (2 wt.-%) into PES-C has a reinforcement effect. With higher concentrations of UHMWPE, the mechanical properties decrease gradually. Structural studies demonstrated that the blends are multiphasic in the whole composition range. The minor UHMWPE, dispersed uniformly and oriented along the flow direction, as well as the strong interfacial adhesion contribute to the increase of the mechanical performance of the blends. The domain size of the UHMWPE phase was found to increase with the increase of its concentration.

Poly(vinyl methyl ether) poly(methyl methacrylate) blends using diblock copolymer of styrene and methyl methacrylate as compatibilizer

Blends of poly(vinyl methyl ether) (PVME) and poly(methyl methacrylate) (PMMA) compatibilized by poly(styrene-block-methyl methacrylate) (P(S-b-MMA)) ale studied by FT-IR, DSC, excimer fluorescence spectrometry, and scanning electron microscopy (SEM). In FT-IR measurement the ratio of absorption intensity at 1107 cm(-1) to that at 1085 cm(-1) (I-1107/I-1085) reaches a minimum at about 10wt% block copolymer content. DSC results show that the glass transition temperature of PVME in the blends has a maximum at 10 wt% copolymer content. In plots of the ratio of excimer-to-monomer fluorescence emission intensities (I-E/I-M) VS block copolymer content, I-E/I-M increases rapidly above 10%. Ail these phenomena show that PS block chains penetrate into PVME: domains on addition of block copolymer. Above 10% copolymer content, block copolymer chains tend to form micelles in bulk phase.

Tensile and transformational behavior of poly(ether sulfone) polycarbonate blends

Blends of a poly(ether sulfone) (PES) and a polycarbonate (PC) were prepared by melt-mixing and were studied by tensile tests, differential scanning calorimetry, dynamic mechanical analysis, density measurements and transmission electron microscopy (TEM). The blends were found to be two-phase systems and an interfacial layer was presumed to be formed between two phases, which was verified by TEM. A synergism of elongation at break and tensile modulus was shown in PES/PC blends. The effects of the crosshead speed on the mechanical properties were discussed for blends with different PES/PC weight ratios.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

Synthesis and properties of block copolymers of poly(ether sulphone)s with liquid crystalline polyester units

Block copolymers of poly(ethersulphone) (PES) oligomers with liquid crystalline polyester units were synthesized by the reaction of dihydroxy-terminated poly(ether sulphone) oligomers (number-average molecular weights: 704, 1,158 and 2570) and terephthaloyl bis(4-oxybenzoyl chloride), and their properties were investigated. The results indicated that the copolymer with PES segments of molecular weight of 704 possessed birefringent features when annealed at 360 degrees C, while the copolymer with PES segments of molecular weight of 2,570 became isotropic. Also, the block copolymers had a better chemical resistance and high-temperature stability than PES.

SYNTHESIS AND CHARACTERIZATION OF A NEW COMB-LIKE POLYMER-BASED ON POLY(VINYL METHYL ETHER-ALT-MALEIC ANHYDRIDE) BACKBONE

A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solvent for the esterification in order to obtain a completely soluble product. The synthesis process was traced through by LR. Compared with the model compounds, the presumed structure of this comblike polymer has been proved to be valid by C-13 NMR The comb polymer is a white rubbery solid. It can be dissolved in butanone and THF, and manifests good film forming ability.

MORPHOLOGY AND DYNAMIC-MECHANICAL PROPERTIES OF NYLON 66/POLY(ETHER IMIDE) BLENDS

The morphology and dynamic mechanical properties of blends of poly(ether imide) (PEI) and nylon 66 over the full composition range have been investigated. Torque changes during mixing were also measured. Lower torque values than those calculated by the log-additivity rule were obtained, resulting from the slip at the interface due to low interaction between the components. The particle size of the dispersed phase and morphology of the blends were examined by scanning electron microscopy. The composition of each phase was calculated. The blends of PEI and nylon 66 showed phase-separated structures with small spherical domains of 0.3 similar to 0.7 mu m. The glass transition temperatures (T(g)s) of the blends were shifted inward, compared with those of the homopolymers, which implied that the blends were partially miscible over a range of compositions. T-g1, corresponding to PEI-rich phase, was less affected by composition than T-g2, corresponding to nylon 66-rich phase. This indicated that the fraction of PEI mixed into nylon 66-rich phase increased with decreasing PEI content and that nylon 66 was rarely mixed into the PEI-rich phase. The effect of composition on the secondary relaxations was examined. Both T-beta, corresponding to the motion of amide groups in nylon 66, and T-gamma, corresponding to that of ether groups in PEI, were shifted to higher temperature, probably because of the formation of intermolecular interactions between the components.