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  • Polymer and Materials Science  (4)
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  • 1
    ISSN: 1022-1336
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: This work reports a comparative study of the catalytic behaviour for a series of metallocenes derived from Ti, Zr, Hf and Nb, which after activation with methylaluminoxane can polymerize ethylene. Results show that the Zr metallocene with a —(CH3)2Si—Bridge presents the highest activity, and the metallocenes based on Hf and Nb do not show any significant activity under the tested conditions.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 19 (1998), S. 409-411 
    ISSN: 1022-1336
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: RuHCl(CO)(PCy3)2 (1) dissolved in 1-butyl-3-methylimidazolium tetrafluoroborate (2) molten salt is able to reduce selectively NBR to HNBR under hydrogen partial pressures between 10 and 40 bar at 100-160°C in a typical two-phase catalytic reaction. Reaction rates between 0.059 (mmol Ru)-1 · min-1 and 1.65 (mmol Ru)-1 · min-1 were obtained depending on the reaction parameters and increasing with the volume of the molten salt. The overall process has an apparent activation energy of 47 ± 3 kJ · mol-1. The recovered ionic catalyst solution can be reused several times without significant changes in the catalytic performance (selectivity and activity).
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The behaviour of catalytic systems based on zirconium compounds for the copolymerization of ethylene with 1-hexene and 1-octene is reported. The metallocenes (CH3)2SiCp2ZrCl2, Cp2ZrCl2 (Cp = η5-cyclopentadienyl), C2H4[Ind]2ZrCl2 and (Ind = η5-indenyl) were chosen for this study. The bridged catalysts, (CH3)2SiCp2ZrCl2 and C2H4[Ind]2ZrCl2, and the metallocene Cp2ZrCl2 showed similar catalytic activities for home- and copolymerization of ethylene with 1-hexene. 13C NMR analysis showed that the composition of copolymerization products depends on the catalytic system, in other words, on the ligand structure of the transition metal. Copolymers obtained using the bridged catalysts have greater incorporation of comonomer. Thermal analysis and viscosity measurements demonstrated that an increase of the comonomer concentration reduces the melting point, the crystallinity and the molecular weight of the copolymer. Results from infrared spectroscopy showed that β-elimination is one of the possible termination reactions. The monomer reactivity ratios r were determined for all catalytic systems using Fineman-Ross and 13C NMR methods. The values of r1 (M1 = ethylene) and r2 (M2 = α-olefin) showed an effect of the type of metallocene and of α-olefin on the structure of the copolymer obtained.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The Zr surface loading from Cp2ZrCl2 toluene solutions on different kinds of commercial silicas (Grace 948, 952 and 956) was determined by Rutherford backscattering spectrometry. In all silicas, a saturation trend was observed with increasing amount of metal in the initial solution, the largest Zr loading value (1 wt.-%) being observed for silica Grace 948. Solid surface areas were determined by the BET method before and after metallocene immobilization, revealing that the values do not change after zirconocene impregnation. Two different kinds of cocatalyst were used, methylaluminoxane and trimethylaluminium. The aluminium loading on silica Grace 948 was determined using the 27Al(p,γ)28Si nuclear reaction and titrometry, both showing that methylaluminoxane leads to an “Al grafting” four times more efficient than does trimethylaluminium. Finally, the catalytic activity of these systems was tested in the polymerization of ethylene. The supported catalysts were shown to be active, specially using the low cost trimethylaluminium as a cocatalyst. The polymers obtained with the supported systems exhibited a higher molecular weight than those obtained with the homogeneous system.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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