Isolation, spectra, structure, and ring-opening polymerization of strained macrocyclic aryl(ether ketone) dimer

Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4'-difluorobenzophenone and easily polymerized to high molecular weight linear poly(ether ketone). The cyclic compound was characterized by FTIR, H-1- and C-13-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of he phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). (C) 1997 John Wiley & Sons, Inc.

The multiple melting behaviour of immiscible poly(ether ether ketone) poly(ether diphenyl ether ketone) blend

Poly(ether ether ketone)/poly(ether diphenyl ether ketone) blend containing 30 wt% PEDEK was used to investigate the melting behaviour of immiscible PEEK/PEDEK blends. The results measured from differential scanning calorimetry (d.s.c.) and wide-angle X-ray diffraction (WAXD) showed that immiscible PEEK/PEDEK blends isothermally crystallized at a temperature between Tg and Tm-2 (PEEK's normal melting point) from the glassy state also exhibited the multi-melting behaviour like poly(aryl ether ketones) homopolymers. In addition, the low-temperature melting peak was independent of composition of poly(aryl ether ketones) blends and only associated with the thermal history. (C) 1997 Elsevier Science Ltd.

The synthesis of a 1,1'-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2'-Bis(3,4-dicarboxyphenoxy)-1,1'-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of I,1'-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255-294 degrees C and 5% weight loss temperatures in the range of 502-541 degrees C in nitrogen and 473-537 degrees C in air. (C) 1997 Elsevier Science Ltd.

The synthesis and thermotropic liquid crystalline behavior of the novel poly(aryl ether ketone)s containing chloro-side group

The novel poly(aryl ether ketone)s containing chloro-side group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and chlorohydroquinone with either 4,4'-difluorobenzophenone(BP/CH/DF) or 1,4-bis(p-fluorobenzoyl)benzene (BP/CH/BF) and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. The thermotropic liquid crystalline behavior was observed in the copolymers containing 50 and 70% biphenol. Melting transition (Tm) and isotropization transition (Ti) both appeared in the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline state. The novel poly(aryl ether ketone)s had relatively higher glass transition temperature (Tg) in the range of 168 similar to 200 degrees C and lower melting temperature (Tm) in the range of 290 similar to 340 degrees C. The thermal stability (Td) was in the range of 430 similar to 490 degrees C.

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

Isothermal melt and cold crystallization kinetics of PEDEKmK linked by meta-phenyl and biphenyl were investigated by differential scanning calorimetry in two temperature regions. Avrami analysis is used to describe the primary stages of the melt and cold crystallization, with exponent n = 2 and n = 4, respectively. The activation energies are -118 kJ/mol and 510 kJ/mol for crystallization from the melt and the glassy states, respectively. The equilibrium melting point T-m(0) is estimated to be 309 degrees C by using the Hoffman-Weeks approach, which compares favorably with determination from the Thomson-Gibbs method. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 8.45 erg/cm(2) and sigma(e) = 45.17 erg/cm(2), respectively. The work of chain folding q is determined as 3.06 kcal/mol. These observed crystallization characteristics of PEDEKmK are compared with those of the other members of poly(aryl ether ketone) family. (C) 1997 John Wiley & Sons, Inc.

Novel poly(aryl ether ketone)s containing various pendant groups .2. Gas-transport properties

The gas transport of hydrogen, oxygen, nitrogen, carbon dioxide, and methane gases in a series of poly(aryl ether ketone)s was examined. These polymer membranes have a wide range of permeability coefficients and permselectivity coefficients, showing excellent gas-transport properties. The enhanced interchain interaction in the polymers due to intermolecular hydrogen bonds and ionic bonds results in a considerable increase in permselectivity but a decrease in permeability. On the contrary, the polymers with bulky arkyl substituents show significantly increased permeability. The causes of this trend are interpreted in terms of the free volume, interchain distance, and glass transition temperature together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest is the observation that the ionomer IMPEK-K+, which simultaneously contains bulky isopropyl substituents and pendant carboxylate groups, exhibits over twice higher CO2 permeability and 15% higher CO2/CH4 permselectivity than those of bisphenol-A p'olysulfone (PSF). The possibility of using the new synthesized poly(aryl ether ketone)s in gas separation membrane application is also discussed. (C) 1997 John Wiley & Sons, Inc.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .2. Poly(ether ether ketone ketone), PEEKK

The crystal structure, morphology and polymorphism induced by uniaxial drawing of poly(ether ether ketone ketone) [PEEKK] have been studied by transmission electron microscopy (TEM), electron diffraction (ED) and wide angle X-ray diffraction (WAXD). On the basis of WAXD and ED patterns,the crystal structure of unoriented PEEKK is determined to have two-chain orthorhombic packing with unit cell parameters of a 0.772 nm, b = 0.600 nm, c = 1.004 nm (form I), A stress-induced crystal modification (form II) is identified and found to possess a two-chain orthorhombic lattice with unit cell dimensions of a = 0.461 nm, b = 1.074 nm, c = 1.080 nm. The 7.5% increase in c-axis dimension for form II is attributed to an overextended chain conformation, arising from extensional deformation during uniaxial drawing and fixed ''in-situ'' through strain-induced crystallization. The average ether-ketone bridge bond angles in form II crystal are determined to be 148.9 degrees by using standard bond lengths. The crystal morphology of PEEKK bears a great similarity to that of PEEK. The crystals grow in the form of spherulites and have the b-axis of unit cell radial. The effects of draw rate on strain-induced crystallization and induction of form II structure are also discussed.

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

Analysis of the nonisothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK) was performed by using differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could describe only the primary stage of nonisothermal crystallization of PEEKK. And, the Ozawa analysis, when applied to this polymer system, failed to describe its nonisothermal crystallization behavior. A new and convenient approach for the nonisothermal crystallization was proposed by combining the Avrami equation with the Ozawa equation. By evaluating the kinetic parameters in this approach, the crystallization behavior of PEEKK was analyzed. According to the Kissinger method, the activation energies were determined to be 189 and 328 kJ/mol for nonisothermal melt and cold crystallization, respectively.

Crystallization process and morphology structure of poly(aryl ether ether ketone ketone) containing meta-phenyl links

The crystallization process and morphology of poly(aryl ether ether ketone ketone) containing meta-phenyl links (PEEKmK) have been investigated by transmission electron microscopy and electron diffraction. The results indicate that the thin films of PEEKmK isothermally crystallized from both the glassy state and the melt at the temperature range of 180 similar to 250 degrees C consist of two kinds of morphological forms, i. e. large (order of mu m), flat-on single crystals and narrow, lath-like, edge-on lamellae, The latter consists of the spherulites. Meanwhile, the growing process of the two kinds of morphological forms has been discussed.

The crystal structure and drawing induced polymorphism in poly(aryl ether ketone)s .3. Crystallization during hot-drawing of poly(ether ether ketone ketone)

The evolution of crystallinity and polymorphism during hot-drawing of amorphous poly(ether ether ketone ketone) (PEEKK) as a function of strain rate, draw ratio, and temperature was investigated. In modification I, the competition of chain extension and molecular alignment is responsible for the strain rate and temperature dependence. Modification II crystallization is basically controlled by chain extension during stretching. The former can be transformed into the latter via relaxation during stretching or annealing at elevated temperature.

The double-melting behavior of poly(ether diphenyl ether ketone)

Poly(ether diphenyl ether ketone) (PEDEK) synthesized by the nucleophilic route has the following chemical structure: [GRAPHICS] At some given temperatures for a given time isothermally crystallized PEDEK sample exhibits two endothermic peaks which are similar to PEEK and PEEKK The melting behavior of PEDEK crystallized from the glassy state is investigated through differential scanning calorimeter (DSC). We consider that the high-melting peak is related to the perfect crystals and the low-melting peak is associated with a few imperfect crystals. (C) 1997 John Wiley & Sons, Inc.

Crystal structure and crystallinity of poly(aryl ether biphenyl ether ketone ketone)

The crystal structure of poly(aryl ether biphenyl ether ketone ketone) (PEDEKK) was determined to comprise a two-chain orthorhombic unit cell with dimensions a 0.778 nm, b = 0.606 nm and c = 2.375 nm by using wide-angle X-ray diffraction (WAXD). According to the orthorhombic system, the 12 reflections of this polymer were indexed. The crystallite size increases with increasing the crystallization temperature. The results of the degree of crystallinity (W-c,W-x) calculated from WAXD were compatible with those from density (W-c,W-d) and calorimetry (W-c,W-h) measurements.

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.

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.

Synthesis and properties of poly(aryl ether ether ketone ketone) containing meta-phenyl links

A Series of poly(aryl ether ether ketone ketone) containing meta-phenyl link were synthesized, the general properties were studied by DSC, stretch, impact, etc.. The results indicated that with the raising of meta linkage monomer fractions, the glass transition point decreased, the melting temperature decreased at first, and then disappeared, but for all-meta-linked polymer, T-m appeared once more. And this kind of polymer had good stretch and impact resistance performance.