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.     

Environment potential in Hartree-Fock-Slater formalism

A new formulation of the environment potential approach (EPA) is developed within the Hartree-Fock-Slater framework. As the results of illustrative applications to C₅ cluster which is the smallest unit of diamond lattice, EPA is shown to annul efficiently the fictitious-surface effects which are inevitably brought into a finite-size-cluster model.     

Effect of electrostatic field on the polymer chain in the quaternized reaction of polyvinylpyridine with alkyl halides

In order to discuss the electrostatic-field effect on a polymer reaction, the quaternization of poly-4-vinylpyridine–benzyl chloride (system I) was compared to that of poly-γ-chloromethylstyrene–γ-picoline (system II). In these two systems, the reaction initially proceeded according to the simple second-order kinetics. However, after the degree of quaternization exceeded 20–30 mole-%, a deviation from simple second-order kinetics occurred. In system I negative deviation occurred, while in system II positive deviation occurred. These phenomena occurred even though the solvent or the initial concentrations of the reactants were changed. The reasons for these phenomena are given below. In system I, the quaternized pyridine nitrogens prevented the benzyl chloride from approaching the unquaternized pyridine nitrogens. However, in system II the free γ-picoline was attracted by the quaternized chloro-γ-methyl site. Furthermore, the point at which the deviation occurred was determined by the degree of chloromethylation. All these results suggest that the effect of an electrostatic field must be presumed in these two systems.     

Development of new cycloaddition reactions based on the unique reactivity of unsaturated hydrocarbons

We discovered that the reactivity of some conjugated and electron-deficient hydrocarbons was quite different in the presence of transition metal catalysts. In this review we report our development and applications of the highly selective palladium and nickel-catalyzed cycloaddition reactions of unsaturated hydrocarbons such as conjugated enynes, electron-deficient allenes, and electron-deficient methylenecyclopropanes. Some homocoupling reactions as well as co-cyclization reactions were described. The efficient synthesis of 4--7 membered carbocycles was achieved.     

Environment potential in closing bonds case

A method of an electronic structure calculation of cluster is suggested. It consists of an “effective” potential with an electron to close the torn valence bonds which appear inevitably in a finite-size-cluster model. The method is applied to the C₅ cluster representing the diamond lattice and is shown to be effective to nullify the pseudo-surface effects.     

Support theorems for random Schrödinger operators

In the multi-dimensional case it is shown that the increase of the topological support of the probability measure describing the randomness of potentials implies the increase of the spectrum. In the one-dimensional case the converse statement for the absolutely continuous spectrum is valid. Especially the spectrum (in general dimension) and the absolutely continuous spectrum (in one-dimension) are determined only by the topological support of the random potentials.Research partially supported by the USNSF under grant MCS-81-20833     

3+2] cross-coupling reactions of aziridines with isocyanates catalyzed by nickel(II) iodide

[reaction: see text]. Cycloaddition of aziridines with isocyanates proceeded smoothly in the presence of a nickel catalyst, and five iminooxazolidine derivatives were isolated in good yields. The best result was obtained when the reaction was carried out in the presence of NiI2, and a longer reaction time allowed the isomerization of the iminooxazolidine to the corresponding imidazolidinone derivatives.     

Hydrogen Intercalation in Potassium-C60

Abstract

Solid state ¹H NMR of (KH)₃C₆₀ was measured in the temperature range between ?80 and 60 °C. A doublet spectrum composed of main peak at ?7.0 ppm and shoulder peak at ～0 ppm was observed at room temperature. The negative chemical shift of the main peak indicates that hydrogen in (KH)₃C₆₀ exists as a hydride-like ion. The 60 °C spectrum became singlet at ?5.8 ppm due to motional narrowing.