Synthesis and characterization of poly[4-(4-hydroxyphenoxy) benzoic acid]

Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc.     

Local composition in binary mixtures of Lennard-Jones fluids with differing sizes of components

Three Lennard-Jones binary liquid mixture systems obeying Lorentz-Berthelot rules, but having differing component sizes and energy parameters, have been used to calculate the local fractions of the two components around each type of central particle over the entire composition range from molecular-dynamics data. It is found that well-defined local fractions can be determined even in the case where the size difference between the particles is large. The results obtained are compared with values predicted by the Wilson and NRTL equations. It is confirmed that the NRTL equation gives satisfactory agreement only in the case of mixtures of components having the same size parameters. A new correlation is proposed by a modification of the NRTL equation. This correlation can predict reasonably well local-fraction data for all the Lennard-Jones liquid mixtures studied so far.     

Alternating-current ionic conduction and dielectric relaxation of poly(vinylidene fluoride) at high temperatures

Dielectric properties of poly(vinylidene fluoride) have been studied in the frequency range 20 Hz to 1 MHz and between 100 and 220°C, during heating and cooling. The dielectric constant and loss change abruptly at the temperature T_m corresponding to the melting point. At lower frequencies, two types of ionic conductin are observed. One appears below T_m and is attributed to interfacial polarization. The other occurs above T_m and is related to electrode polarization. These results suggest that a crystalline polymer is a heterogeneous medium for ionic transport, while the melt is a homogeneous medium. From these results, the nature of ac ionic conduction in crystalline polymers is discussed. At high frequency, the α relaxation is observed below T_m. It is due to the molecular motion in the crystalline region and disappears at T_m.     

Crystal structure, phase transition and anisotropic thermal expansion of barium zirconium diorthophosphate, BaZr(PO4)2

The crystal structure of BaZr(PO₄)₂ at 298 K was determined from conventional X-ray powder diffraction data using direct methods, and it was further refined by the Rietveld method. The structure was monoclinic (space group C2/m, Z=2) with , , , β=93.086(1)° and . Final reliability indices were R_wp=8.21%, R_p=5.64% and R_B=2.92%. The atom arrangement is similar to that of yavapaiite (KFe(SO₄)₂), however, these crystal structures differ distinctly in the coordination numbers of barium and potassium atoms; the former is tenfold coordinated, whereas the latter is sixfold coordinated. The powder specimens were also examined by high-temperature XRD and DTA to reveal the occurrence of a phase transition from monoclinic to orthorhombic at 732 K during heating. Upon cooling the reverse transition occurred at 710 K. The monoclinic crystal expanded almost one-dimensionally along [503] during the heating process. The orthorhombic phase also showed a tendency to expand one-dimensionally along the c-axis above 732 K.     

Alternating copolymerization of polar vinyl monomers in the presence of zinc chloride. II. Properties of acrylonitrile–styrene copolymer

The properties of the acrylonitrile–styrene copolymer prepared in the presence of zinc chloride were investigated in comparison with those of a copolymer having the same overall composition and prepared by the ordinary radical procedure. The characteristics of the polymer prepared with ZnCl₂ were as follows: (1) less coloration by alkali treatment, (2) less coloration by thermal treatment and (3) higher glass transition temperature. These features may be attributed principally to the structure of the copolymer, which has more unlike bonds and less long sequences as described in the first article of this series. The effects of residual salt in the copolymer on the properties were also investigated.     

Rhodium-catalyzed allyl transfer from homoallyl alcohols to aldehydes via retro-allylation followed by isomerization into ketones

Retro-allylation of homoallyl alcohol by rhodium catalysis occurs to generate allylrhodium species. This allylrhodium reacts with aldehydes to give the corresponding secondary alcohols in situ. Isomerization of these alcohols proceeds in the same pots to furnish the corresponding saturated ketones in good yields. [reaction: see text]