A HIGH-RESOLUTION SOLID-STATE NMR AND DSC STUDY OF MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY(VINYL ALCOHOL)/POLY(N-VINYL-2-PYRROLIDONE) BLENDS

Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVPy) were studied by C-13 cross-polarization/magic angle spinning (CP/MAS) n.m.r. and d.s.c. The C-13 CP/MAS spectra show that the blends were miscible on a molecular level over the whole composition range studied, and that the intramolecular hydrogen bonds of PVA were broken and intermolecular hydrogen bonds between PVA and PVPy formed when the two polymers were mixed. The results of a spin-lattice relaxation study indicate that blending of the two polymers reduced the average intermolecular distance and molecular motion of each component, even in the miscible amorphous phase, and that addition of PVPy into PVA has a definite effect on the crystallinity of PVA in the blends over the whole composition range, yet there is still detectable crystallinity even when the PVPy content is as high as 80 wt%. These results are consistent with those obtained from d.s.c. studies.

BLENDS OF POLY[3,3-BIS(CHLOROMETHYL)OXETANE] WITH POLY(VINYL ACETATE) .1. THERMAL AND MECHANICAL-PROPERTIES

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T(g)). The T(g) of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a beta-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations.

TENSILE PROPERTIES OF BLENDS OF POLY(ETHER SULFONE) WITH A POLY(ETHER IMIDE)

Blends of poly(ether sulphone) (PES) with a poly(ether imide) (PEI) in various proportions were prepared by the coprecipitation method. Mechanical properties and morphology of the blends were studied using tensile tests and scanning electron microscopy (SEM). The tensile moduli exhibit positive deviations from simple additivity. Marked positive deviations were also observed for ultimate strength. These results suggest that the PEI/PES blends are mechanically compatible. SEM study revealed that the blends are not homogeneous and the polymers are immiscible on the segmental level. However, the dispersions of the blends are rather fine. The interfaces between the two phases are excellently bonded; PEI and PES appear to interact well.

MISCIBILITY OF POLY(N-VINYL-2-PYRROLIDONE) WITH POLY(ETHER SULFONE) AND 2 PHENOLPHTHALEIN-BASED POLYMERS

Blends of poly(N-vinyl-2-pyrrolidone) (PVP) with poly(ether sulphone) and two phenolphthalein-based polymers, viz. phenolphthalein poly(ether ether sulphone) and phenolphthalein poly(ether ether ketone) were prepared by casting from a common solvent and studied by differential scanning calorimetry. It was found that all the PVP blends are miscible and show a single, composition-dependent glass transition temperature (T(g)). The T(g)-composition dependence has been analysed by the use of the Gordon-Taylor equation. The values of the k parameter in the Gordon-Taylor equation obtained are all not high for the three pairs, in accordance with the fact that there is no strongly specific interaction between PVP and any of the other polymers.

TENSILE PROPERTIES OF BLENDS OF PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) WITH A POLY(ETHER IMIDE)

Blends of phenolphthalein poly(ether ether ketone) (PEK-C) with a poly(ether imide) (PEI) in various proportions were prepared by the coprecipitation method. Mechanical properties and morphology of the blends were studied using tensile tests and scanning electron microscopy (SEM). It was found that the tensile moduli exhibit positive deviations from simple additivity. Marked positive deviations were also observed for ultimate strength. These results suggest that the PEI/PEK-C blends are mechanically compatible. SEM study shows no evidence of phase separation, supporting the idea that the blends are compatible.

CRYSTALLIZATION OF POLY(ARYL-ETHER-ETHER-KETONE)S BLENDS

The crystallization and melting behaviour of poly(aryl-ether-ether-ketone) (PEEK) in blends with another polymer of the same family containing a bulky pendant phenolphthalein group (PEK-C) have been investigated by thermal methods. The small interaction energy density of the polymer pair (B = -8.99 J/cm3), evaluated from equilibrium melting point depression, is consistent with the T(g) data that indicate partial miscibility in the melt. Two conjugated phases are in equilibrium at 430-degrees-C: one is crystallizable and contains about 35 wt% of PEK-C; the other, containing only 15 wt% of PEEK, does not form crystals upon cooling and it interferes with the development of spherulites in the sample. The analysis of kinetic data according to nucleation theories shows that crystallization of PEEK in the explored temperature range takes place in Regime III and that a transition to Regime II might be a consequence of an increase in the amount of non-crystallizable molecules in the PEEK-rich phase. A composition independent value of the end surface free energy of PEEK lamellae has been derived from kinetic data (sigma-e = 40 +/- 4 erg/cm2) in excellent agreement with previous thermodynamic estimates. A new value for the equilibrium melting temperature of PEEK (T(m)-degrees = 639 K) has been obtained; it is about 30-degrees-C lower than the commonly accepted value and it explains better the "memory effect" in the crystallization from the melt of this high performance polymer.