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     

Cationic ring-opening polymerization of 2-phenyl-1,2-oxaphospholane (deoxophostone)

Summary The ring-opening polymerization of deoxophostone 5, a five-membered cyclic phosphinite, has been studied. Some cationic initiators gave polymer whereas anionic and radical initiators as well as metal chloride (Lewis acid) catalysts did not yield polymer. The polymer consisted of a phosphine oxide repeating unit 6. The polymerization proceeded via the Arbuzov-type reaction. The reduction of polymer 6 with a HSiCl₃/Et₃N system gave polyphosphine 7.     

Fischer–Tropsch synthesis over Co–SiO2 catalysts prepared by the sol–gel method

Fischer–Tropsch synthesis was carried out in slurry phase over uniformly dispersed Co–SiO₂ catalysts prepared by the sol–gel method. When 0.01–1 wt.% of noble metals were added to the Co–SiO₂ catalysts, a high and stable catalytic activity was obtained over 60 h of the reaction at 503 K and 1 MPa. The addition of noble metals increased the reducibility of surface Co on the catalysts, without changing the particle size of Co metal significantly. High dispersion of metallic Co species stabilized on SiO₂ was responsible for stable activity. The uniform pore size of the catalysts was enlarged by varying the preparation conditions and by adding organic compounds such as N,N-dimethylformamide and formamide. Increased pore size resulted in decrease in CO conversion and selectivity for CO₂, a byproduct, and an increase in the olefin/paraffin ratio of the products. By modifying the surface of wide pore silica with Co–SiO₂ prepared by the sol–gel method, a bimodal pore structured catalyst was prepared. The bimodal catalyst showed high catalytic performance with reducing the amount of the expensive sol–gel Co–SiO₂.     

Reply to the Comment by K. Jorgensen et al. to “Analysis of constant rate period of spray drying of slurry”

Previously developed model for spray drying of slurry droplets with high solid content (Liang, 2001) was revised to describe correctly a boundary condition on the outer surface of droplet on basis of the rate of liquid evaporation.     

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.     

Effects of functional groups in glow discharge polymerization

Summary Glow discharge polymerizations of allyltrimethylsilane (ATMS) and trimethylvinyloxysilane (TMVOS) were investigated by elemental analysis and infrared spectroscopy. The formed polymers were far different in elemental composition from the starting materials, and possessed high carbon and hydrogen contents. There was less difference in an infrared-spectral sense between the two polymers from ATMS and TMVOS. A polymer-forming process in a discharge state is discussed.     

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.     

Multi-step precipitation separation system using mixture of thermosensitive polymers

Summary Multi-step precipitation separation system was developed by using aqueous mixtures of some thermosensitive polymers. The following three polymers were used here; poly(N-n-propylacrylamide), poly(N-isopropylacrylamide), and poly(N-isopropylmethacrylamide). A mixture of the three polymers showed three endothermic peaks, and the peak top temperatures were almost consistent with that of the each polymer solution. The polymers were purified by thermal precipitation to obtain fractions which can respond in narrow temperature ranges prior to use. In the case of the precipitation separation of two polymers mixtures, purities of the obtained precipitate and supernatant fractions became high comparing with the case in which the unpurified polymers were used. Parts of the polymers which were not the precipitation targets were also precipitated by the separation procedures. This was caused not only by insolubilization of the non-targeted polymers due to their phase transitions but also by their non-specific entanglement with the targeted polymers. The purities of the fractions also improved when the difference of the phase transition temperature between two polymers was large enough to avoid the coprecipitation. In the case of the precipitation separation of mixtures of the three polymers, purities of each fraction also improved when the purified polymers were used.     

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.