Cationic ring-opening polymerization of 2-phenyl-1,3,6,2-trioxaphosphocane

Summary The ring-opening polymerization of 2-phenyl-1,3,-6,2-trioxaphosphocane (4), an eight-membered cyclic phosphonite, has been investigated. Cationic initiators of PhCH₂-Cl and MeOTf gave polymers, whereas anionic and radical initiators did not yield polymer. The structure of polymer was examined by IR, ¹H, ³¹P, and ³¹C NMR spectroscopy of polymers and elemental analysis as well as the alkaline hydrolysis products. The polymer consisted of two different units, i.e., the major part is the normal phosphinate structure 5 and the minor part is the isomerized unit 6 in 7% with PhCH₂Cl initiation and in 34% with MeOTf initiator. The difference in nature of propagating species from these two initiators are discussed in connection with their reactivities.On leave from the Institute of Chemistry, Academia Sinica, Beijing, China     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Design of High-Quality Pt–CeO2 Composite Anodes Supported by Carbon Black for Direct Methanol Fuel Cell Application

A Pt on nano-sized CeO₂ particles that in turn are supported on carbon black (CB) was synthesized using the co-impregnation method. This potential anode material for fuel cell applications was synthesized in a stepwise process. The pure CeO₂ was synthesized using an ammonium carbonate precipitation method, and the Pt particles dispersed on the CeO₂ in such a way that a uniform dispersion with the CB was obtained (Pt–CeO₂/CB). The electrochemical activity of the methanol (CH₃OH) oxidation reaction on the Pt–CeO₂/CB was investigated using cyclic voltammetry and chronoamperometry experimentation. The onset potential of CH₃OH oxidation reaction on the Pt–CeO₂/CB anode was shifted to a lower potential as compared with that on commercially available Pt–Ru/carbon (C) alloy anode. In addition, the activation energy of the Pt–CeO₂/CB anode was much lower than that of the Pt–Ru/C alloy anode. Moreover, the current density of the Pt–CeO₂/CB anode was much higher than that of the Pt–Ru/C alloy anode at temperatures between 28° and 60°C. These results suggest that the anode performance of the Pt–CeO₂/CB anode at the operating temperature of typical fuel cells (80°C) is superior to that of the more usual Pt–Ru/C alloy anode. Importantly, the rare metal, Ru, is not required in the present anode material and the amount of Pt required is also significantly reduced. As a consequence, we report a promising candidate Pt–CeO₂/CB composite anode for application in the development of direct methanol fuel cells.     

Influence of dry operating conditions: observation of oscillations and low temperature CO oxidation over Co3O4 and Au/Co3O4 catalysts

A Sm(III) exchanged NaY zeolite prepared from aqueous SmCl₃ was modified with various amounts of fluorine using NH₄F. These fluorinated zeolites exhibit enhanced catalytic activity for the dealkylation of cumene. The evaluation of acid sites by infrared spectroscopy and pyridine adsorption was correlated with fluorine content.     

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.     

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.