HELIX-INDUCED ASYMMETRIC POLYMERIZATION

Asymmetric polymerization could be induced by an already formed optically active living prepolymer with one-handed screw sense helix conformation. The usually formed anionic active centre on the prepolymer could be changed to cationic, radical and even of Ziegler-Natta type. These living prepolymers with various kinds of active centre were all effective to induce a consequent asymmetric polymerization of a monomer which may be other than that in the prepolymer, to afford an optically active helical chain with the same screw sense as that of the prepolymer. Eight monomers have been used in the work. Optical rotation, circular dichroism and gelpermeation chromatography have been taken to prove the helix-induced asymmetric polymerization.

CRYSTALLIZATION KINETICS OF MIXTURES OF POLY(EPSILON-CAPROLACTONE) AND POLY(STYRENE-CO-ACRYLONITRILE)

The crystallization kinetics in mixtures of poly(epsilon-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) has been investigated as the function of composition and crystallization temperature. The isothermal growth rates of PCL spherulites decrease with increasing concentration of SAN. Because of the miscibility of PCL/SAN mixtures, the radial growth rates of the spherulites are described by a kinetic equation including the interaction parameter and the free energy for the formation of crystal nuclei. The interaction parameter obtained from the fitting of the kinetic equation with experimental data is in good agreement with that obtained from melting point depression. Folding surface free energies decrease with the increase of SAN concentration. In light of these results, it is suggested that, for the PCL/SAN mixtures, the noncrystallizable SAN polymer reduces the mobility of crystallizable PCL polymer so that the growth rates decrease with the increase of noncrystallizable component fraction.

RADIATION-INDUCED CROSS-LINKING OF AROMATIC POLYMERS WITH A CARDO GROUP

The effects of irradiation on some members of the family of aromatic polymers with a cardo group, such as polyetherketone with a cardo group (PEK-C) and polyethersulfone with a cardo group (PES-C), were studied. It was found that PEK-C and PES-C can be crosslinked by irradiation under vacuum. Moreover, it was also found that the intensity of the shake-up peak of x-ray photoelectron spectroscopy (XPS) for PEK-C and PES-C varies with irradiation dose. Gelation doses (Rg) of PEK-C and PES-C were estimated from the XPS shake-up peak.

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.

CONFORMATION OF PHENYL RINGS IN THE HELICAL CHAIN POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The conformation of phenyl rings in the side groups of the helical chain polymer poly(tripenyl-methyl methacrylate) (1) in solution was studied by spectroscopic methods. According to the Raman spectrum the phenyl rings of 1 and triphenylmethyl methacrylate in solution have the same depolarization ratio at 1002 cm-1. The electronic spectra (ultraviolet and fluorescence) of 1 are similar to those of model substances, except for the "red shift" of the spectra of about 5 nm. It was concluded that the phenyl rings can rotate around the phenyl-C bond.

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.

SEM STUDY ON FRACTURE-BEHAVIOR OF ETHYLENE/PROPYLENE BLOCK COPOLYMERS AND THEIR BLENDS

The toughening effect of the separate phases of ethylene/propylene block copolymers and their blends was studied by scanning electron microscopy (SEM). The results obtained show that the interfacial adhesion between separate phases and the isotactic polypropene (iPP) matrix in ethylene/propylene block copolymers is strong at room temperature, but poor at low temperature; specimens exhibit tearing of separate phases during fracture at room temperature, but interfacial fracture between separate phases and the iPP matrix at low temperature. From the characteristics of fractographs of ethylene/propylene block copolymers and their blends, it could be concluded that the separate phases improve the toughness of specimens in several ways: they promote the plastic deformation of the iPP, and they can be deformed and fractured themselves during the fracture process. However, it was shown that the plastic deformation processes, such as multiple-crazing, shear yielding, etc. of the matrix are the dominant mechanisms of energy absorption in highly toughened ethylene/propylene block copolymers and their blends. The deformation and fracture of separate phases are only of secondary importance.

FACTOR-ANALYSIS APPLIED TO X-RAY-DIFFRACTION DIAGRAMS OF POLYMER BLENDS

The feasibility of applying the method of factor analysis to X-ray diffraction diagrams of binary blends of polypropylene and ethylene-propylene-diene terpolymer (PP/EPDM) was examined. The result of mathematical treatment was satisfactory. The number of scattering species and their concentrations in six kinds of PP/EPDM blends were determined. The separation of the spectral peaks of each species in the blends, contributing spectral intensities, was carried out.

RELATIONSHIP OF THE SEQUENCE DISTRIBUTION OF A POLYMER TO THE CATALYTIC ACTIVITY OF ITS ND COMPLEX

The sequence distribution of the monomeric units in the styrene-acrylic acid copolymer has been obtained by calculation. The probability of long sequences of styrene increases with an increase in the content of the monomer in the copolymer. The highest distribution of short sequences of styrene takes place for the copolymer containing equimolecular amounts of styrene and acrylic acid. The copolymer which has this latter structure is inadequate for the synthesis of highly active supported complexes. When the distributions of long and short sequences of styrene are approximately equal, the activity of the Nd and Fe prepared polymer complexes is higher.

STUDIES ON RADIATION EFFECTS OF PTFE .2. RADIATION-INDUCED STRUCTURAL-CHANGES AND THE TEMPERATURE EFFECT

In this work PTFE sheets irradiated with gamma-rays at 150-degrees-C and 200-degrees-C were studied using x-ray photoelectron spectroscopy (XPS). The main structural changes in PTFE due to radiation are the formation of CF3 and CF groups. An irradiation temperature dependence of the relative content of the three kinds of groups in irradiated PTFE was observed. The CF3 groups, especially when irradiation is carried out a lower temperatures, can defluorinate in the same manner as previosly reported for CF2 groups. The CF groups, on the other hand, are observed to increase with increasing irradiation dose and irradiation temperature; the latter was explained as due to an increase in branching structures.