NMR investigation of phenolphthalein polyether ether ketone .1. The chain structure and assignments of H-1, C-13 NMR lines of PEK-C

Amorphous samples of polyether ketone with cardo(PEK-C) have been studied in the solution state by C-13, H-1 high-resolution NMR, The H-1 and C-13 1D NMR spectra were assigned using two dimensional chemical shift correlated spectroscopy, 2D homonuclear correlated(COSY) and heteronuclear correlated (HETCOR) spectroscopy present important information. In this work, the structural units of PEK-C was determined by NMR. For some peaks, these assignments are confirmed by two dimensional long-range heteronuclear correlation experiments, A little modification is made on the original C-13 peak assignments for the main chain, The symmetry and the isotacticity of the chain structure for PEK-C are obvious on NMR data.

Crystal structure and its transition for poly(aryl ether ketone ketone)s .1.

Poly(aryl ether ketone ketone)s (PEKK) was a high-performance engineering plastics, By means of Wide Angle X-ray Diffraction (WAXD) and Differential Scanning Calorimetry (DSC) methods, PEKK samples crystallized in solvent induction, from glass state and from melting state were studied, Crystal forms I and II for PEKK were found, The formation of crystal form II was dependent on thermal history and solvent induction, and this form II had melting point 10 degrees C or so lower than that of form I crystallized from glass state, All PEKK samples had low melting peaks which were relevant to the polarization of PEKK molecular chain, while they had nothing to do with thermal history, The heat of fusion for PEKK low melting peaks accounted for,percentage of 2 to 10 or so of the whole heat of fusion, And PEKK has its equilibrium melting point of 409 degrees C.

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

A series of poly(aryl ether ketone)s containing meta-phenyl links are synthesized, DSC and wide-angle X-ray scattering, etc, are used to study the general properties of the polymers, With the increasing of meta linkage monomer percentage, the melting temperature decreases sharply at first, then rises steadily, the glass transition point. keeps a stable value, and crystallin;ty and crystallizing rate are reduced, A part of amorphous film of the polymer is annealed at different temperatures, DSC scan shows that besides T-m, a new melting peak (T-m') at low temperature appears, And with heat treating temperature rising, T-m' shifts to high temperature, and T-m keeps a stable value.

Miscibility of poly(ether ether ketone)/poly(ether diphenyl ether ketone) blends

Poly(ether ether ketone) and poly(ether diphenyl ether ketone) homopolymers are prepared by nucleophilic substitution routes. Miscibility of PEEK/PEDEK blends has been studied by wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (d.s.c.). The results indicate that for PEEK/PEDEK blends, when the PEDEK content (weight fraction) is greater than 0.20 and less than 0.75, PEEK and PEDEK components form independent crystalline regions, i.e. they are immiscible; when the PEDEK content is in the range W-PEDEK less than or equal to 0.20 or greater than or equal to 0.75, a rich PEEK- or PEDEK-rich content crystallizes from a mixed melt and PEEK and PEDEK are miscible. Copyright (C) 1996 Elsevier Science Ltd.

Crystal packing of poly(ether ketone ketone)

The crystal structure of poly(ether ketone ketone) (PEKK) is predicted by using Cerius2 software according to the wide angle X-ray diffraction (WAXD) experiment result. The predicted structure has a planar zigzag chain conformation between ether oxygen and ketone carbons in an orthorhombic lattice. Average zigzag angle is 126 degrees and average torsion angle is 30.32 degrees. The WAXD powder pattern calculated from the crystal packing model is in good agreement with the experiment result.

Crystallization behavior of poly(ether ether ketone ketone)

The melting behavior of semicrystalline poly(ether ether ketone ketone) (PEEKK) has been studied by differential scanning calorimetry (DSC). When PEEKK is annealed from the amorphous state, it usually shows two melting peaks. The upper melting peaks arise first, and the lower melting peaks are developed later. The upper melting peaks shown in the DSC thermogram are the combination (addition) of three parts: initial crystal formed before scanning; reorganization; and melting-recrystallization of lower melting peaks in the DSC scanning period. In the study of isothermal crystallization kinetics, the Avrami equation was used to analyze the primary process of the isothermal crystallization; the Avrami constant, n, is about 2 for PEEKK from the melt and 1.5 for PEEKK from the glass state. According to the Lauritzen-Hoffman equation, the kinetic parameter of PEEKK from the melt is 851.5 K; the crystallization kinetic parameter of PEEKK is higher than that of PEEK, and suggests the crystallizability of PEEKK is less than that of PEEK. The study of crystallization on PEEKK under nonisothermal conditions is also reported for cooling rates from 2.5 degrees C/min to 40 degrees C/min, and the nonisothermal condition was studied by Mandelkern analysis. The results show the nonisothermal crystallization is different from the isothermal crystallization. (C) 1996 John Wiley & Sons, Inc.

Studies on the fusion heat of poly(ether ether ketone ketone)-poly(ether biphenyl ether ketone ketone) copolymers

On the basis of DSC measurements, the Delta H-f(0) values of the fusion heat for PEEKK-PEBEKK copolymers with various biphenyl contents were obtained by using thermodynamics statistical theory proposed by Flory and graphical method of the specific volume-fusion heat. The results reveal that Delta H-f(0) values determined by these two methods for PEEKK-PEBEKK copolymers with various biphenyl content are nearly the same, and that Delta H-f(0) values are closely dependent on biphenyl content. Delta H-f(0) value is minimum at n(B)=0.35.

Effect of heat treatment on the parameters of crystal structure and degree of crystallinity of poly(aryl-ether-ether-ketone)

The variations of unit cell parameters and crystallite size of nine PEEK samples treated at various temperatures have been studied by using Wide-Angle X-ray Diffraction (WAXD), The results indicate a decrease in unit cell parameter a,b and c but an increase in crystallite size L(hkl) With the increase beat treatment temperature. Based on X-ray scattering intensity theory and using the graphic multipeak resolution method, the formula of degree of crystallinity (W-c,W-X) for PEEK is derived. The results calculated are compatible with the density measurement and calorimetry.

Morphological studies on a novel poly(aryl ether ketone)

The morphology of a novel poly(aryl ether ketone) [PEDEKmK] was investigated via polarizing optical microscopy (POM), TEM, DSC, SAXS and electron diffraction (ED). A distinct change in lamellar thickness, orientation, and spherulitic morphology was observed due to crystal melting and recrystallization. However, the crystal packing mode is found to be identical before and after the recrystallization process.

Tension-tension fatigue failure behaviour of poly(phenylene ether ketone) (PEK-C)

Tension-tension fatigue tests were conducted on unnotched injection moulded poly(phenylene ether ketone) (PEK-C) specimens with two stress ratios, R. The fatigue behaviour of this material is described. The S-N curves (S = alternating stress, N = number of cycles to failure) for different R values have the same general shape, but the curve for bigger R is shifted to long cycles. A fatigue lifetime inversion is observed from constructed S-N curves. Examinations of failure surfaces and analyses of the fatigue data reveal that the fatigue failure mechanism of the material studied is crack growth dominated. But the manner of the fatigue crack initiation and propagation depends on the maximum cyclic stress applied. At higher stresses, the fatigue crack originates at the corner of the specimen and propagates inward; at lower stresses, the fatigue crack nucleates at an internal flaw of the specimen and propagates outward. The fatigue lifetime inversion corresponds to the transition of crack initiation and propagation from one mode to the other. Copyright (C) 1996 Elsevier Science Ltd.

Dynamic light-scattering characterization of the molecular weight distribution of a broadly distributed phenolphthalein poly(aryl ether ketone)

Using a recently developed laser light-scattering (LLS) procedure, we accomplished the characterization of a broadly distributed unfractionated phenolphthalein poly(aryl ether ketone) (PEK-C) in CHCl3 at 25 degrees C. The laplace inversion of precisely measured intensity-intensity time correlation function from dynamic LLS leads us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). By using a previously established calibration of D (cm(2)/s) = 2.37 X 10(-4)M(-0.57), were able to convert G(D) into a differential weight distribution f(w)(M). The weight-average molecular weight M(w) calculated from f(w)(M) agrees well with that directly measured in static LLS. Our results indicate that both the calibration and LLS procedure used in this study are ready to be applied as a routine method for the characterization of the molecular weight distribution of PEK-C. (C) 1996 John Wiley & Sons, Inc.

Miscibility and crystallization behaviour of poly(ether ether ketone)/polyimide blends

The miscibility and crystallization behaviour of the blends of poly(ether ether ketone) (PEEK) with two thermoplastic polyimides (PI), PEI-E and YS-30, prepared by solution blending were studied by the use of small-angle X-ray scattering (SAXS), differential scanning calorimetry (d.s.c.) and polarizing microscopy techniques. The results obtained show that PEEK/YS-30 is miscible, while PEEK/PEI-E is partially miscible only in the composition range with PEI-E content up to 20 wt%. The crystallization behaviour of PEEK in PEEK/PI blends depends on the crystallization condition of the blend sample as well as the chemical structure and the content of the PI added. Our SAXS results indicate that the segregation of PI molecular chains during crystallization of PEEK chains in the blends is interfibrillar for PEEK/PEI-E blends, but interlamellar for PEEK/YS-30 blends. The compatibility and the crystallization behaviour are discussed in terms of charge transfer interaction between PI and PI molecules and between PI and PEEK molecules.

Laser light-scattering study of novel thermoplastics .2. Phenolphthalein poly(ether sulfone) (PES-C)

Five narrowly distributed fractions of phenolphthalein poly(ether sulfone) (PES-C) were studied in CHCl3 by both static and dynamic laser light scattering (LLS) at 25 degrees C. The dynamic LLS showed that the PES-C samples contain some large polymer clusters as in previously studied phenolphthalein poly(ether ketone)(PEK-C). These large clusters can be removed by a 0.1-mu m filter. Our results showed that [R(g)(2)](1/2)(z) = (3.35 +/- 0.13) x 10(-2) M(w)((0.52 +/- 0.03)) and [D] = (2.26 +/- 0.02) x 10(-4)M(w)-((0.54) +/- 0.03)) with [R(g)(2)](1/2)(z), M(w) and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.45 +/- 0.04) x 10(-4)M-((0.55 +/- 0.05)), where D and M correspond to monodisperse species. Using this scaling relationship, we have successfully converted the translational diffusion coefficient distribution into the molecular weight distribution for each of the five PES-C fractional The weight-average molecular weights obtained from dynamic light scattering have a good agreement with that obtained from static laser light-scattering measurements.

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.