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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2049-2056 
    ISSN: 0887-624X
    Keywords: metallocenes ; olefin polymerizations ; Ziegler-Natta catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Propylene was polymerized with rac-ethylene-bis (1-η5-indenyl)dichlorozirconium/methylaluminoxane in solvents of different polarity. The poly (propylene) formed was separated by solvent extraction; 13C-NMR and DSC measurements were made on the polymer fractions. The poly(propylene) in each solvent fraction has its characteristic molecular weight steric pentad distributions, melting transition temperature, and enthalpy for fusion irrespective of the polymerization medium. The results suggest that the medium dielectric constant does not affect the polymerization rate or the intrinsic stereoselectivity, propagation and chain transfer rates a given catalytic species but can alter the occurrence of steric insertion errors through shifting of distributions of the propagating species producing poly(propylenes) of different stereoregularities. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Tab.
    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 32 (1994), S. 2387-2393 
    ISSN: 0887-624X
    Keywords: zirconocene ; Ziegler-Natta catalysts ; stereospecific olefin polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Propylene was polymerized by binary zirconocenium catalysts derived from rac-ethylenebis(1-η5-indenyl)dimethylzirconium and cation forming agents (C6H5)3C+(C6F5)4B- and (C6F5)3B. Polymerizations were also performed with the ternary systems of Et[Ind]2ZrCl2, Et3Al, and the cation forming agents. The catalyst systems, with the inert noncoordinating counter-ion, (C6F5)4B-, have much higher activity and stereoselectivity than the ones with the CH3B-(C6F5)3 counter-ion. Much less active still are catalysts having BF4- or (C6H5)4B- counter-ions. Similar but smaller effects of counter-ion structure on ethylene polymerization were observed. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0887-624X
    Keywords: Ziegler-Natta catalysts ; ansa-metallocene catalyst ; thermoplastic elastomeric poly(propylene) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic-anti-[ethylidene(1-η5-tetramethylcyclopentadienyl) (1-η5-indenyl)dimethyltitanium (6) has been synthesized and its molecular structure determined by x-ray diffraction methods. The two Ti=Me(1) and Ti=Me(2) units have bond distances differing by 0.08 Å and their proton NMR resonances are separated by over 1 ppm. Using this compound and methylaluminoxane (MAO) as the activator, at 25°C the 6/MAO catalyst produced polypropylene having crystalline domain with physical crosslinks. The polymers obtained at lower polymerization temperatures are rheologically liquids. The behaviors of this catalyst system resembles closely the previously reported rac-[anti-ethylidene(1-η5-tetramethylcyclopentadienyl) (1-η5-indenyl)dichlorotitanium (4)/MAO system. The structure of 6 determined here furnishes tangible support for the proposed two-state (isomeric)-switching propagation mechanism. Addition of MAO to 6 causes broadening of the Me(1) resonance in the 1H-NMR spectra, and 6 is decomposed by Ph3C+B(C6F5)-4. © 1992 John Wiley & Sons, Inc.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1747-1754 
    ISSN: 0887-624X
    Keywords: zirconocene ; supported TiCl3 ; Ziegler-Natta catalysts ; hexene polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MgCl2-supported TiCl3 catalysts, with and/or without electron donor modifier (internal Bi or external Be), were compared with rac-ethylenebis(indenyl)zirconium dichloride (1) activated with either MAO or the cation forming agent, triphenyl carbenium tetrakis(pentafluorophenyl)borate (2), with triethylalumium (TEA). The activities of the heterogeneous catalysts depend on the presence or absence of the Lewis base, were relatively insensitive to the temperature of polymerization, and produce poly(hexene) with molecular weights up to 106. The 1/MAO catalyst has about five times higher activity at 50°C but is almost inactive at -30°C; the overall activation energy is 12.4 kcal mol-1. In contrast, the activity for hexene polymerization by the 1/2/TEA catalyst is actually slightly greater at lower temperature. The MW's of poly(hexene) obtained with the zirconocenium catalysts are only in the tens of thousands because of rapid β-hydride elimination by the electrophilic cationic Zr center. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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