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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2945-2953 
    ISSN: 0887-624X
    Keywords: metallocene ; Ziegle-Natta catalysis ; syndioselective polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of reaction conditions, including catalyst concentration, temperature, and immobilization on support, have been investigated for syndioselective propylene polymerization by the “bare” zirconocenium ion generated from 1,1-diphenyl-methylidene(1-η5-cyclopentadienyl)(9-η5-fluorenyl)zirconium-dichloride precursor (2). Neither variation of the catalyst concentration nor immobilization of 2 on silica support affect the syndiospecificity of polymerization. The stereoregularity of the syndiotactic polypropylene, as judged from the melting transition temperature and homosteric r-pentad population by 13C-NMR, were found to be proportional to polymer molecular weight. These behaviors are compared with a typical isoselective catalyst ethylenebis(4,5,6,7-tetrahydroindenyl) Zr precursor (4). They are in close resemblance in the case of the S-enantiomeric complex of 4, but the racemic mixture of 4 is markedly inferior. The origins of stereo- and regio-errors are discussed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2093-2108 
    ISSN: 0887-624X
    Keywords: zirconocene ; ethylene polymerization ; propylene polymerization ; silica-supported catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(1-indenyl)-di[1′S, 2′R, 5′S)-methoxy]silane (1) was converted into a mixture of corresponding ansa-diastereomeric zirconocenes. Further purification afforded a single dia-stereomer, di[(1′S, 2′R, 5′S)-methoxy] silylene-bis[η5-1(R, R)-(+)-indenyl] dichlorozirconium (2), which is optically active and hydrocarbon soluble. Extremely rapid ethylene, propylene, and ethylene-hexene polymerizations were observed both in toluene and n-heptane solutions; for instance, at 50°C, activity for ethylene polymerization reaches ∼ 1.5×1010 (g of PE/((mol of Zr) · [C2H4] · h). The “bare” zirconocenium ion generated from 2/TIBA/Ph3CB(C6F5)4 exhibits unusual polymerization behaviors; the polymerization activity increases monotonically with temperature of polymerization (Tp) up to a conventional polymerization condition (50-70°C), and the 13C NMR study shows that the isotactic poly-propylene obtained has fairly high [mmmm] methyl pentad distributions at high Tp (≤25°C with [mmmm] ∼ 0.93-0.75) and a perfect stereoregularity at low Tp (≤0°C with [mmmm] 〉 0.99). The catalyst precursors 2 and Et(Ind)2ZrCl2 (3) supported on silica by different approaches produced poly(olefins) of different molecular weights and stereoregularities, and a methylaluminokane and Ph3CB(C6F5)4 free silica-supported zirconocene system was found to be activated by triisobutylaluminum. © 1995 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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