Magnesium chloride supported high mileage catalysts for olefin polymerization. XXI. Isospecific and regiospecific vanadium catalyst for propylene polymerization

Several CW–V catalysts were prepared by supporting VCl₄ on Mg Cl₂ with ethyl benzoate and CH–V catalysts prepared by reacting MgCl₂.ROH, phthalic anhydride, and VCl₄. These vanadium catalysts, activated with TEA (triethyl aluminum)/MPT (methyl-p-toluate) produce mainly (88–96%) refluxing n-heptane insoluble isotactic PP. The active site has $ k_{p,i} = 1580 \left( M {\rm s} \right)^{ - 1}, k_{tr,i}^{\rm A} = 2 \times 10^{ - 3} {\rm s}^{ - 1} , k_{tr}^{\rm H} = 3.8 \times 10^{ - 2} \left( {\rm torr} \right)^{ - {1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm s}^{ - 1}$ for the isospecific ones and $ k_{p,a} = 58 \left( M {\rm s} \right)^{ - 1} ,k_{tr,a}^{\rm A} = 3 \times 10^{ - 3} {\rm s}^{ -1}$ for the nonspecific sites. Catalyst of VCl₃ supported on MgCl₂ has comparable productivity as the VCl₄/MgCl₂ catalyst but catalyst of VCl₂ supported on MgCl₂ exhibit only one-ninth of the productivity. Extensive comparison has been made between the CW–V and the CW–Ti systems which revealed striking similarities between their polymerization behaviors. MgCl₂ exerts profound influence on the stereochemical control of the vanadium ion on its activity for monomer coordination and insertion.     

Asymmetric Diels-Alder Reactions of Chiral Menthyl α-Sulfinylacrylates

Introducing two chiral auxiliaries, sulfoxide and menthol, into an acrylate would have either matched or mismatched pair systems. The presence of chiral menthol in α-sulfinylacrylates can change the diastereoselectivity from 24% d.e. to a single diastereomer by manipulation of the double asymmetric strategy.     

Application of BGO detector to monitor in situ16N concentration in a reactor pool

A high efficiency BGO detecting system coupled to a coolant pumping device was used to monitor on-line the 6.13 MeV high energy gamma-ray, which is emitted from the 7.1 s half-life of¹⁶N activated by¹⁶O(n, p) reaction in a nuclear reactor. The system has been demonstrated effectively to monitor the real-time reactor power level as well as the space-time neutron flux distribution in reactor coolant.     

Multicomponent polymer coating to block photocatalytic activity of TiO2 nanoparticles

Chemical grafting of anti-oxidant molecules with an additional hydrophobic polymer coating directly onto TiO(2) particle surfaces, using sonochemistry, is found to eliminate photocatalytic degradation enabling highly effective screening against UV radiation.     

X‐Ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation States in Fe–NO Complexes

Extensive study of the electronic structure of Fe‐NO complexes using a variety of spectroscopic methods was attempted to understand how iron controls the binding and release of nitric oxide. The comparable energy levels of NO π* orbitals and Fe 3d orbitals complicate the bonding interaction within Fe? NO complexes and puzzle the quantitative assignment of NO oxidation state. Enemark–Feltham notation, {Fe(NO)_x}ⁿ, was devised to circumvent this puzzle. This 40‐year puzzle is revisited using valence‐to‐core X‐ray emission spectroscopy (V2C XES) in combination with computational study. DFT calculation establishes a linear relationship between ΔE_σ2s*‐σ2p of NO and its oxidation state. V2C Fe XES study of Fe? NO complexes reveals the ΔE_σ2s*‐σ2p of NO derived from NO σ_2s*/σ_2p→Fe_1s transitions and determines NO oxidation state in Fe? NO complexes. Quantitative assignment of NO oxidation state will correlate the feasible redox process of nitric oxide and Fe‐nitrosylation biology.     

Synthesis,Characterization and Photoluminescence of Lanthanide Metal‐organic Frameworks,Constructed from Triangular 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate Ligands

Eight isomorphous metal‐organic frameworks: [Ln₂(TATAB)₂(H₂O)(DMA)₆]·5H₂O (Ln = Sm ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), Dy ( 5 ), Er ( 6 ), Tm ( 7 ), Yb ( 8 )); TATAB = 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate, DMA = N,N‐dimethylacetamide), were synthesized by the self‐assembly of lanthanide ions, TATAB, DMA and H₂O. Single‐crystal X‐ray crystallography reveals they are three dimensional frameworks with 2‐fold interpenetration. Solid‐state photoluminescence studies indicate ligand‐to‐metal energy transfer is more efficient for compounds 2 and 4 which exhibit intense characteristic lanthanide emissions at room temperature.     

Syntheses and flame retarding properties of DOPO polymers,melamine polymers,and DOPO‐melamine copolymers

The 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) polymers, melamine polymers, and DOPO‐melamine copolymers have been successfully synthesized, and their flame retarding properties have also been investigated by blending with polypropylene (PP)/styrene‐ethylene‐butylene‐styrene (SEBS) alloys. Experimental results establish that all of them are good polymeric flame retardants. No blooming or color stains occur when they are incorporated into PP/SEBS alloys. Among lab‐made polymeric flame retardants, DOPO‐ melamine copolymers exhibit the best thermal stability and nonflammability. PP/SEBS alloys containing DOPO‐melamine copolymers display comparable thermal resistance and flame retarding behavior (T_d = 290°C; char yield: 15.6%, LOI: 23, and flammability: UL‐94 V0) as the alloys containing common commercial flame retardants (i.e., DOPO, melamine, and ammonium polyphosphate). Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrogenation of olefins in supercritical CO(2) catalyzed by palladium nanoparticles in a water-in-CO(2) microemulsion

Nanometer-sized metallic palladium particles can be synthesized by hydrogen reduction of Pd2+ ions dissolved in the water core of a water-in-CO2 microemulsion. The Pd nanoparticles, stabilized by the micromeulsion and uniformly dispersed in the supercritical fluid phase, are effective catalysts for hydrogenation of olefins. Examples of rapid and efficient hydrogenation of water-soluble and CO2-soluble olefins catalyzed by the Pd nanoparticles in supercritical CO2 are given.     

Inclusion of SWCNTs in Nb/Pt co-doped TiO2 thin-film sensor for ethanol vapor detection

Nb-Pt co-doped TiO₂ and the hybrid SWCNTs/Nb-Pt co-doped TiO₂ thin films have been prepared by the sol–gel spin-coating process for gas-sensor fabrication. Field emission scanning electron microscope (FE-SEM, TEM and X-ray diffraction (XRD) characterizations indicated that the SWCNTs inclusion did not affect the morphology of the TiO₂ thin film and the particle size. Additionally, the SWCNTs were well embedded in the TiO₂ matrix. The gas-sensing properties of Nb–Pt co-doped TiO₂ thin films with and without SWCNTs inclusion were investigated. The hybrid sensors with the inclusion of different SWCNTs contents are examined to elucidate the effect of SWCNTs content on the gas-sensing properties. Experimental results revealed that the responses to ethanol of Nb–Pt co-doped TiO₂ sensors with SWNCTs inclusion increase by factors of 2–5 depending on the operating temperature and the ethanol concentration, compared to that of the sensor without SWCNTs inclusion. Moreover, all hybrid sensors can operate with high sensitivity and stability at a relatively low operating temperature (<335 °C). The responses of the hybrid sensors are greatly affected by SWCNTs content inclusion. The optimized SWCNTs content of 0.01% by weight was obtained for our experiment. The improved gas-sensing performance should be attributed to the additional formation of the p/n junction between SWCNTs (p-type) and TiO₂ (n-type).