Studies on catalysis by molten metals. 14. Catalytic cracking of asphalts at low temperature

The catalytic effects of liquid metals for low-temperature (336 °C) asphalt-cracking have been examined using a semi-batch reactor. All the liquid metals examined (Bi, Cd, Ga, In, Pb and Sn) effectively catalysed the reduction of molecular weight with minimal gasification (<1 wt%). Gasification had a positive correlation with the reduction in molecular weight in the processed asphalts. The catalytic activities of liquid metals tor these two reactions were proportional to a parameter which represents the interaction between the atoms of the catalyst metal and the radicals formed in the course of the reaction. Mass flow among four fractions (saturates, aromatics, resins and asphaltenes) had two independent paths: conversion of resins to saturates and of aromatics to asphaltenes. The former path dominated when catalytic dehydrogenation activity was relatively low, whereas the latter dominated when the catalytic activity was high.     

Chemospecific ring-opening polymerization of α-methylenemacrolides

α-Methylenemacrolides having various groups, such as aromatic, ether, and amine, were enzymatically, anionically, and radically polymerized. The polymerization with the lipase catalyst successfully afforded polymers only through the ring-opening process, whereas the vinyl polymerizations selectively proceeded by using anionic and radical initiators. The polyesters obtained by the enzymatic polymerization have a polymerizable methacrylic methylene group in the main-chain, in addition to the aromatic and polar groups, and were further radically polymerized to quantitatively produce a cross-linked polymer gel.     

An apparent ensemble effect in the oxidative coupling of methane on hydroxyapatites with incorporated lead

The introduction of small quantities of lead into calcium hydroxyapatite catalysts produces marked increases in the selectivity to C₂₊ hydrocarbons, while the conversion of methane remains relatively constant. Small surface concentrations of lead are sufficient to achieve C₂₊ selectivities of 80 and 90%, with oxygen and nitrous oxide, respectively, in contrast with 18 and 46%, respectively, obtained in the absence of lead. Since surface concentration of lead species sufficient to stabilize pairs of methyl radicals in close proximity to each other would be expected to facilitate the formation of C₂ hydrocarbons, an ensemble effect appears to be extant.     

Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Characterization of styrene–methyl methacrylate–n-butyl acrylate terpolymers. II. Effects of sequence distribution on glass transition temperature

The effects of sequence distribution on the glass transition temperature (T_g) of the title terpolymers prepared by radical polymerization were studied. T_g was examined by thermomechanical analysis. The average diad concentrations, as estimation of sequence distributions were calculated from monomer reactivity ratios. A modified Gibbs–Dimarzio equation for binary copolymers was extended to terpolymers to explain the relation between observed T_g and average diad concentrations. The observed T_g showed good agreement with the calculated values determined by the extended equation.     

Deposition of dense isotropic carbon from acetylene in fluidized bed

Pyrolytic carbon was deposited from acetylene in a fluidized bed at 1100°C on alumina microspheres. In case when only argon was used as the diluent gas, density and BAF of the deposit decreased and deposition yield increased with increasing acetylene concentration. Hydrogen sypply suppressed carbon formation and, consequently, caused an increase in density and Lc. BAF was relatively independent of hydrogen concentration. It was found that high density, isotropic carbon can be deposited from acetylene at 1100°C, if an appropriate proportion of hydrogen is added.     

Change of the amorphous state by heat treatment below the glass transition temperature

This study was undertaken to elucidate the state of a polymer in the amorphous state through a change of motion of the molecular chain caused by heat treatment below the glass transition temperature. From dielectric measurements of amorphous poly(ethylene terephthalate) heat-treated below T_g, it was found that the average relaxation time, the distribution of relaxation time and the dielectric strength increase with increase of heat treatment. From these results, it was concluded that the amorphous state becomes more random by heat treatment.     

Studies of tetrazoles as rubber chemicals. II. Reactivities and antioxidation activities of reactive antioxidants based on tetrazoles

The chemical reactivities of novel reactive antioxidants based on tetrazoles for carbon–carbon double bonds of liquid polybutadiene and their antioxidation activities toward isoprene rubber were evaluated. These antioxidants, i.e., 2-substituted phenyl-5-(3′,5′ -di-tert-butyl-4′-hydroxyphenyl)tetrazoles (PHPT), were pyrolyzed in liquid polybutadiene at 160–170°C for 30 min to attach to rubber in extents of 61–85% of the nitrileimines formed from PHPT by 1,3-dipolar addition reaction. The reactivities of PHPT followed the order p-Cl > m-Cl > H > p-CH₃ > m-CH₃, p-OC₂H₅, suggesting that PHPT reacts with diene rubber in electrophilic reaction and p-derivatives exhibit higher contents of binding than m-derivatives due to steric hindrance. From oxygen absorption data, the antioxidation activities of PHPT for isoprene rubber vulcanizates followed the order m-Cl, m-CH₃ > H, p-Cl, p-Cl, p-CH₃ > p-OC₂H₅. Isoprene rubber vulcanizates, obtained after pretreatment with PHPT by heating, were extracted with acetone, followed by aging to show that there was good retention and appreciable antioxidation activities of PHPT, especially, p-CH₃ and p-Cl substituted PHPT.     

Anodic Dissolution of Uranium Mononitride in Lithium Chloride-Potassium Chloride Eutectic Melt

Uranium-plutonium nitride is a candidate fuel for fast reactors, but its major drawback is ¹⁴C formation from natural nitrogen. One would probably have to use highly ¹⁵N-enriched nitrogen. A pyrochemical process with molten-salt electroreflning has been proposed as a means to increase the nuclear proliferation resistance of the fuel cycle. Molten-salt electroreflning could also be applied to nitride fuels to make possible the recycling of ¹⁵N. The anodic dissolution behavior of UN in LiCI-KCI melt was studied to provide the basis for a feasibility study of electroreflning of irradiated nitride fuels.