Macrocyclic oligomeric arylene ether ketones: Synthesis and polymerization

Some novel macrocylic(arylene ether ketone)oligomers were synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-dinitrobenzophenone with bisphenols in the presence of anhydrous potassium carbonate under pseudo-high-dilution conditions. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), H-1 NMR and FT-IR confirmed their cyclic nature and the compositions of the oligomeric mixtures was indicated by GPC analysis. Ring-opening polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 52.3 and M-n of 17.2 k was achieved by heating at 280 degrees C for 40 min in the presence of a nucleophilic initiator.

Novel poly(aryl ether ketone)s exhibiting liquid crystallinity

Novel poly(aryl ether ketone)s were synthesized by nucleophilic substitution reactions of difluoromonomer with 4,4'-biphenol and substituted hydroquinone. The results showed that the novel polymers exhibited multiple phase transitions and formed optical birefringence textures above their melting transitions.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone). V: Estimation of temperature distribution during cure process

A numerical method to estimate temperature distribution during the cure of epoxy-terminated poly(phenylene ether ketone) (E-PEK)-based composite is suggested. The effect of the temperature distribution on the selection of cure cycle is evaluated using a suggested alternation criterion. The effect of varying heating rate and thickness on the temperature distribution, viscosity distribution and distribution of the extent of cure reaction are discussed based on the combination of the here-established temperature distribution model and the previously established curing kinetics model and chemorheological model. It is found that, for a thin composite (<=10mm) and low heating rate (<=2.5K/min), the effect of temperature distribution on cure cycle and on the processing window for pressure application can be neglected. Low heating rate is of benefit to reduce the temperature gradient. The processing window for pressure application becomes narrower with increasing thicknesses of composite sheets. The validity of the temperature distribution model and the modified processing window is evaluated through the characterization of mechanical and physical properties of E-PEK-based composite fabricated according to different temperature distribution conditions.

Studies on fracture morphology of short carbon fiber reinforced poly(phenylene ether ketone)(SCF/PEK-C) composites

The shear fracture morphology of SCF/PEK-C composite with carbon fibers treated for different times was studied carefully by SEM. The result shows that the adhesion between fiber and matrix was improved and fractured model also changed from interface fracture to brittle fracture with increasing treatment time of carbon fiber. The fracture mechanism was discussed preliminary.

Nonradiative energy transfer study on the interface of compatibilized linear low density polyethylene/poly(methyl methacrylate) blends

Blends of chromophore-labeled LLDPE and chromophore-labeled PMMA compatibilized by block copolymer of hydrogenated polybutadiene and methyl methacrylate (PHB-b-PMMA) were studied by nonradiative energy transfer (NRET) technique. The ratio of fluorescence intensity of the donor at 336 nm and the acceptor at 408 nm (I-D/I-A) decreased with an increase in block copolymer content. At about 8 wt.-% block copolymer content I-D/I-A reached a minimum value, indicating the interdiffusion of LLDPE chains and PMMA chains in the interface is strongest. The influence of temperature on the interdiffusion of polymer chains in the interface was also examined. Samples quenched in liquid nitrogen from 140 degrees C showed lower energy transfer efficiencies than those annealed from 150 degrees C to room temperature.

Compatibilization of blends of polybutadiene and poly(methyl methacrylate) with poly(butadiene-block-methyl methacrylate)

Compatibilization of blends of polybutadiene and poly(methyl methacrylate) with butadiene-methyl methacrylate diblock copolymers has been investigated by transmission electron microscopy. When the diblock copolymers are added to the blends, the size of PB particles decreases and their size distribution gets narrower. In PB/PMMA7.6K blends with P(B-b-MMA)25.2K as a compatibilizer, most of micelles exist in the PMMA phase. However, using P(B-b-MMA)38K as a compatibilizer, the micellar aggregation exists in PB particles besides that existing in the PMMA phase. The core of a micelle in the PMMA phase is about 10 nm. In this article the influences of temperature and homo-PMMA molecular weight on compatibilization were also examined. At a high temperature PB particles in blends tend to agglomerate into bigger particles. When the molecular weight of PMMA is close to that of the corresponding block of the copolymer, the best compatibilization result would be achieved. (C) 1998 John Wiley & Sons, Inc.

The synthesis and thermotropic liquid crystalline behaviour of novel main chain poly(aryl ether ketone)s containing a lateral phenyl group

Novel main chain poly(aryl ether ketone)s containing a lateral phenyl group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and phenylhydroquinone with either 4,4'-difluorobenzophenone or 1,4-bis(4-fluorobenzoyl)benzene and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. Thermotropic liquid crystalline behaviour was observed in the copolymers containing 50 and 70mol% biphenol. Melting (T-m) and isotropization (T-i) transitions both appeared on the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline nematic state. As expected, each of the copolymers had a relatively lower melting transition than the biphenol-based homopoly(aryl ether ketone)s because of the copolymerization effect of the crystal-disrupting monomer phenylhydroquinone.

Nonisothermal crystallization behavior of a novel poly(aryl ether ketone): PEDEKmK

Nonisothermal melt crystallization kinetics of PEDEKmK linked by meta-phenyl and biphenyl was investigated by differential scanning calorimetry (DSC). A convenient and reasonable kinetic approach was used to describe the nonisothermal melt crystallization behavior, and its applicability was verified when the modified Avrami analysis by the Jeziorny and Ozawa equation were applied to the crystallization process. The crystallization activation energy was estimated to be -219 kJ/mol by Kissinger method while crystallizing from the PEDEKmK melt nonisothermally. These observed crystallization characteristics were compared to those of the other members of poly(aryl ether ketone) family. (C) 1998 John Wiley & Sons, Inc.

Morphology and structure of poly(aryl ether ketone ketone) containing isophthaloyl moieties crystallized from dilute solution

Spherulites and lamellar single crystals of poly(aryl ether ketone ketone) containing isophthaloyl moieties (PEKK(I)) were obtained from dilute alpha-chloronaphthalene solution. The morphology and structure of the spherulites and single crystals were studied by electron microscopy and electron diffraction. The spherulites were found to consist of elongated lamellar branches that grow with the b crystallographic axis in the radial direction. Single crystals possess a similar habit, with b parallel to the long axis, a transverse, and c perpendicular to the lamellae plane. High-resolution images of the PEKK(I) crystals which show the perfection of and defects in the crystals, were obtained, and many defects or dislocations a,ere observed. (C) 1997 Elsevier Science Ltd.

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.

Preparation of methyl tert-butyl ether (MTBE) over heteropoly acids immobilized on activated carbon (HPA/C) in the vapor phase

Heteropolyacids (HPAs) supported on the activated carbon (SiW12/C and PW12/C) have been used to study the formation of methyl tert-butyl ether (MTBE). Compared to the conventional commercial catalysts, Amberlyst-15 resin and HZSM-5, HPAs supported catalysts have been proved to have much higher catalytic activity under lower temperature, especially selectivity to MTBE is up to 100%. It may be due to the high acid strength of HPAs as well as the specialty of heteropolyanion.

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.

Isothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK)

Isothermal melt and cold crystallization kinetics of PEEKK have been investigated by differential scanning calorimetry in two temperature regions. During the primary crystallization process, the relative crystallinity develops with a time dependence described by the Avrami equation, with exponent n = 2 for both melt and cold crystallization. The activation energies are -544.5 and 466.7 kJ/mol for crystallization from the melt and amorphous glassy state, respectively. The equilibrium melting point T-m(o) is estimated to be 371 degrees C by using the Hoffman-Weeks approach. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma=10 erg/cm(2) and sigma(e) = 60 erg/cm(2), respectively. The work of chain folding q is determined as 3.98 kcal/mol. These observed crystallization kinetic characteristics of PEEKK are compared with those of PEEK. (C) 1997 Elsevier Science Ltd.