STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMER MIXTURES

A statistical thermodynamics theory of polydisperse polymer blends based on a lattice model description of a fluid is formulated. Characterization of a binary polydisperse polymer mixture requires a knowledge of the pure polymer system and the interaction energy. It is assumed that the intrinsic and interactive properties of polymer (for example, T*, P*, rho*, and epsilon(ij)*) are independent of molecular size. Thermodynamic properties of ternary and higher order mixtures are completely defined in terms of the pure fluid polymer parameters and the binary interaction energies. Thermodynamic stability criteria for the phase transitions of a binary mixture are shown. The binodal and spinodal of general binary systems and of special binary systems are discussed.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

PHASE-BEHAVIOR IN EPOXY-RESIN CONTAINING PHENOLPHTHALEIN POLY(ETHER ETHER SULFONE)

Phenolphthalein poly(ether ether sulphone) (PES-C) was found to be miscible with uncured bisphenol-A-type epoxy resin, i.e. diglycidyl ether of bisphenol A (DGEBA), as shown by the existence of a single glass transition temperature within the whole composition range. Miscibility between PES-C and DGEBA is considered to be due mainly to the entropy contribution. However, dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM) studies revealed that PES-C exhibits different miscibility with four cured epoxy resins (ER). The overall compatibility and the resulting morphology of the cured blends are dependent on the choice of cure agent. For the blends cured with amines (4,4'-diaminodiphenylmethane (DDM) and 4,4'-diaminodiphenylsulphone (DDS)), no phase separation occurs as indicated by either d.m.a. or SEM. However, for the blends cured with anhydrides (maleic anhydride (MA) and phthalic anhydride (PA)), both d.m.a. and SEM clearly show evidence of phase separation. SEM study shows that the two phases interact well in the MA-cured blend while the interface between the phases in the PA-cured blend is poorly bonded. The differences in the overall compatibility and the resulting morphology between the amine-cured and anhydride-cured systems have been discussed from the points of view of both thermodynamics and kinetics.

THE COMPATIBILITY AND CRYSTALLIZATION OF THE MIXTURES OF POLY (TETRAHYDROFURAN-b-METHYL METHACRYLATE) DIBLOCK COPOLYMER WITH POLYVINYL CHLORIDE HOMOPOLYMER

The compatibility and crystallization behaviour of the mixtures of poly (tetrahydrofuran-methyl methacrylate) diblock copolymer (PTHF-b-PMMA) with polyvinyl chloride has been studied. We found that the compatibility of these blends, in which there is special interaction between the homopolymer and the PMMA block of the copolymer, is much better than that of the AB/A type blends; and that the crystallization rate and crystallinity of PTHF microdomain changed greatly due to the swollen by PVC homopolymer. In this paper, these changes in cryatallization are well explained according to the theories of block copolymer blends and the density gradient model presented by JIANG Ming.

MISCIBILITY OF POLY(HYDROXYETHER OF PHENOLPHTHALEIN) WITH POLY(ETHER SULFONE)

Blends of poly(hydroxyether of phenolphthalein) (PHP) with poly(ether sulphone) (PES) were prepared by casting from a common solvent; they were found to be miscible and show a single, composition-dependent glass transition temperature. All the PHP/PES blends exhibited lower critical solution temperature behaviour, i.e. phase separation occurred at elevated temperatures. A F.T.-i.r. study revealed that a hydrogen-bonding interaction occurs between these polymers but it is weaker than in pure PHP. The observed miscibility is hence proposed to be the result of specific interactions between the polymers.

CRITERION OF POLYMER POLYMER MISCIBILITY DETERMINED BY VISCOMETRY

The criteria of polymer-polymer miscibility determined by viscometry are reviewed, and a new criterion is proposed based on the classical Huggins equation and the Huggins coefficient K(m) in the blends. It was found that, in a ternary (polymer-A)-(polymer-B)-solvent system, [GRAPHICS] In the absence of strong specific interaction forces between molecules that would encourage aggregation and at sufficiently low concentration, the above equation can be written thus: [GRAPHICS] This equation can be used to determine the miscibility of polymer blends, when: alpha greater-than-or-equal-to 0 miscible, alpha < 0 immiscible. It is found that the new criterion is reasonable and suitable to predict polymer-polymer miscibility by the viscometry method.

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.

PHASE-SEPARATION IN ANHYDRIDE-CURED EPOXY-RESIN CONTAINING PHENOLPHTHALEIN POLY(ETHER ETHER KETONE)

Dynamic mechanical analysis and scanning electron microscopy were used to study phase separation of three blends of anhydride-cure bisphenol-A-type epoxy resin with phenolphthalein poly(ether ether ketone). Phase separation was observed for all the blends. The overall compatibility and the resulting morphology of the cured blends are dependent on the choice of cure agent. The phenomena have been discussed from the points of view of both thermodynamics and kinetics. The effects of the choice of hardener on phase separation are considered to be primarily due to differences between the chemical natures of the hardeners.

DYNAMIC SCALING OF THE STRUCTURE-FUNCTION FOR SPINODAL DECOMPOSITION IN CRITICAL AND NONCRITICAL MIXTURES OF POLY(VINYL ACETATE) POLY(METHYL METHACRYLATE)

The dynamics of phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by using a time-resolved light-scattering technique. In the later stages of spinodal decomposition, a simple dynamic scaling law was found for the scattering function S(q, t)(S(q, t) approximately I(q, t)): S(q, t)q(m)-3 S approximately (q/q(m)). The scaling function determined experimentally was in good agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X8) for critical concentration, and approximately in agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X6) for non-critical mixtures. The light-scattering invariant shows that the later stages of the spinodal decomposition were undergoing domain ripening.

EPITAXIAL CRYSTALLIZATION OF TRANS-1,4-POLYBUTADIENE ON HIGHLY ORIENTED ISOTACTIC POLY(PROPYLENE) FILMS

Epitaxial crystallization of trans-1,4-polybutadiene (PBD) on highly oriented isotactic poly(propylene) (iPP) has been investigated at different crystallization temperatures and rates. From electron microscopy and electron diffraction, it is confirmed that epitactic growth of the low-temperature modification (monoclinic) with microcrystals of PBD on the iPP films takes place with their chain directions about +/- 50-degrees apart. No epitaxial relationship occurs between the high-temperature modification (hexagonal) of PBD and the iPP substrate. Thermal analyses of PBD-PP layered films indicate that the epitaxy has an important effect on the formation of the high-temperature modification of PBD.

EPITAXIAL CRYSTALLIZATION OF SYNDIOTACTIC POLYPROPYLENE ON UNIAXIALLY ORIENTED POLYETHYLENE

The epitaxial crystallization of syndiotactic polypropylene (sPP) on uniaxially oriented polyethylene (PE) has been investigated by electron microscopy and electron diffraction. It is found that the sPP lamellae grow epitaxially on the PE substrate film with the preference in sPP for the b axis as the fast growth direction. Instead of 50-degrees as in the system of isotactic polypropylene with PE, the molecular chains of the sPP crystals are approximately +/- 37-degrees inclined to the chain direction of PE.

THE RING-BANDED SPHERULITE STRUCTURE OF POLY(EPSILON-CAPROLACTONE) IN ITS MISCIBLE MIXTURES WITH POLY(STYRENE-CO-ACRYLONITRILE)

The structure of the PCL spherulite in poly(epsilon-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends was investigated by optical microscopy and small angle light scattering. The spherulite structure with a Maltese cross has been observed in pure PCL. Similar PCL/SAN blends exhibited not only spherulites with a Maltese cross, but also distinct extinction rings. The H(v) light scattering pattern especially caused diffraction rings in PCL/SAN blends but not in pure PCL. The spherical symmetry of spherulite PCL becomes more incomplete and the twist of the lamella becomes more irregular with increasing SAN content. It is found that the spherulite structure of PCL/SAN blends is dependent on the crystallization temperature and the concentration of SAN in PCL/SAN blends.

MISCIBILITY OF POLY(N-VINYL-2-PYRROLIDONE) WITH A COPOLYAMIDE

Blends of poly(N-vinyl-2-pyrrolidone) (PVP) with a copolyamide (CoPA) randomly composed of 1:1:1 (wt) nylon 6, nylon 66 and nylon 610 structural units were prepared by casting from a common solvent. They were found to be miscible and show a single, composition-dependent glass transition temperature (T(g)). The addition of PVP to CoPA significantly lowers the crystallinity owing to an increasing T(g) of the system. The observed miscibility is proposed to be the result of specific interactions between the proton acceptor groups of PVP and the amide groups of CoPA.

STRUCTURE AND PROPERTIES OF SEQUENTIALLY POLYMERIZED PROPYLENE-B-[ETHYLENE-CO-PROPYLENE]-B-PROPYLENE COPOLYMERS

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using delta-TiCl3-Et2AlCl as a catalyst system. The results indicate that the intrinsic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP / EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.

RADIATION-INDUCED CROSS-LINKING OF POLY(METHYL METHACRYLATE)-POLY(ETHYLENE OXIDE) BLEND

Radiation-induced crosslinking of poly(methyl methacrylate) (PMMA)-poly(methylene oxide) (PEO) blends was studied. It was found that PMMA in PMMA-PEO blend can be crosslinked in the range of certain doses (1 approximately 20 x 10(4) Gy) and composition (PMMA% = 30 approximately 70) under the absence of oxygen. Moreover, it was also found that the crosslinking degree of PMMA in the blend in which the content of PMMA is 70% is the largest. The crosslinking degree of PMMA in the blend is closely related with the polymer miscibility. The crosslinking degree of the blend prepared at 60-degrees-C is far higher than one at ambient temperature.