Effects of thermal modification on the structural properties of thermotropic liquid crystalline copolyester and phenoxy resin blends

The effects of thermal modification on the structural properties were studied for a poly(ethylene terephthalate-co-p-hydroxybenzoic acid) liquid crystal bended with phenoxy resin. Poor miscibility and phase separation between the blend components are observed by the temperature dependence of dynamic mechanical properties of sample molded at 260°C, over the composition range studied. The miscibility of the blends is increased by molding at 280°C, and the blends molded by increasing the processing time show a dynamic mechanical transition to a homogeneous blend. These changes are the result of an interchange reaction between the blend components. A rubbery modulus has been observed for such blends. This implies the formation of cross-linked structures that accompany the interchange reactions.     

Effect of applying voltage on photocatalytic destruction of 1,4-dioxane in aqueous system

In the current work, we prepared a TiO₂ coating on stainless mesh using electrophoretic deposition (EPD), and applied voltage to a stainless mesh to examine the synergy effect on photocatalysis of both 1,4-dioxane and ethylene glycol diformate (EGDF), a main intermediate of the photocatalysis of 1,4-dioxane. The photocatalytic decomposition rate of 1,4-dioxane depends on applying voltage under diffusion-limited reaction conditions. Ethylene glycol diformate and 1,4-dioxane exhibited inverse voltage dependence. Voltage swing provides high-efficiency photocatalysis of 1,4-dioxane while suppressing EGDF formation. This method will be effective for a photocatalysis system containing several chemicals, each with different voltage dependence.     

Synthesis of Cubic Boron Nitride from Boron Nitride Synthesized by Pressure Pyrolysis of Borazine

Cubic BN was synthesized under high-temperature and -pressure conditions from BN powder formed by pressure pyrolysis of borazine below 700°C and 100 MPa. The conversion of BN powder to cubic BN was strongly influenced by the residual hydrogen identified by the BH/BN ratio of IR absorption band. The activation energy for cubic BN synthesis from BN powder-20 mol% AIN was 46 kJ/mol, when the starting BN was synthesized at 250°C. A mixture of BN powder and cubic BN particles was converted to cubic BN in a 100% yield by heat treatment at 1800°C and 6.5 GPa without any catalyst. The presence of cubic BN particles does enhance the conversion to cubic BN from BN powder. The energy required for the transformation of starting BN to cubic BN in the presence of cubic BN seed was 355 kJ/mol.     

Enantio-differentiating hydrogenation of prochiral ketones over modified nickel

This article reviews the enantio-differentiating hydrogenation of prochiral ketones over a asymmetrically modified catalyst, focusing on the hydrogenation of simple prochiral alkanones. The parameters affecting catalytic activity and enantiodifferentiating ability are considerable in number, and each parameter should be optimized in order to attain a highperformance enantio-differentiating catalyst. Optimization of the parameters and the mode of enantio-differentiation are discussed and compared with the enantio-differentiating hydrogenation of β-ketoesters.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Template synthesis of novel porous carbons using various types of zeolites

As previously reported, high surface area microporous carbons with long-range order can be synthesized by using zeolite Y as a template. In this work, an attempt is made to synthesize porous carbon using several other types of zeolites (zeolite β, ZSM-5, mordenite and zeolite L). Special attention is paid to whether the structural regularity of each zeolite can be transferred to the carbon structure as well as with the case of zeolite Y. The carbon filling method was then examined to see which gives the highest regularity to the carbon structure. It has been found that the optimum carbon filling method for zeolite Y is not an optimum one for the other zeolites and the degree of the regularity of long-range ordering in the carbons strongly depends on zeolite type. The order of the regularity in the resultant carbons is zeolite β>>zeolite L>mordenite>ZSM-5. The effect of zeolite type on the regularity is discussed in relation to the size and the shape of the zeolite channels.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

Free primary alcohols in oils and waxes from germs,kernels and other components of nuts,seeds, fruits and cereals

The composition of free primary alcohols in oils and waxes obtained from the germ, kernel, seed coat, shell and skin (peel) of various nuts, seeds, fruits and cereals and from the chrysalis of silkworm was examined. These alcohols are usually present in small amounts, along with large quantities of hydrocarbons, esters and glycerides in oils and waxes. Thus, it is necessary to remove hydrocarbons, esters and glycerides to analyze the alcohols. We found that preparative reverse-phase thin-layer chromatography (TLC) was the best way to isolate alcohols from oils and waxes. Gas liquid chromatography (GLC) then detected hexacosanol, octacosanol and triacontanol in the oils and waxes. Octacosanol usually was the predominant alcohol. Relationships between the organs from nuts, seeds, fruits and cereals and the contents of octacosanol are suggested. For example, degermed kernels contained two times more octacosanol than the germ, and the skin coat and shell contained one-half and one-fortieth the octacosanol of the germ, respectively.