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  • 1970-1974  (4)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 413-424 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromocene catalyst for ethylene polymerization shows a high response to hydrogen which leads directly to highly saturated polyethylenes containing methyl groups as the major terminal functionality in the polymers. At a polymerization temperature of 90°C the ratio of termination rate constants for hydrogen (kH) and ethylene (kM) is kH/kM = 3.60 × 103. The ratio of kH to the chain propagation constant (kp) is kH/kp = 4.65 × 10-1 A simple relation that can be derived from polymerization kinetics and the Quackenbos equation exists between melt index and hydrogen-ethylene ratio. A deuterium isotope effect (kH/kD) = 1.2 was calculated for the termination reaction. The overall polymerization process has an apparent activation energy of 10.1 kcal/mole. Oxygen addition studies show catalyst activity is proportional to initial divalent chromium content.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1549-1558 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal aging of a chromocene catalyst, (C5H5)2Cr/SiO2, in an inert atmosphere leads to a modified catalyst which shows poor response to hydrogen as a transfer agent. Polyethylenes prepared at a polymerization temperature of 90°C with this modified catalyst have a low melt index and high vinyl unsaturation level. By thermogravimetry the weight loss of the catalyst, relative to dehydrated silica, was equivalent to loss of one cyclopentadienyl ligand per chromium site. Pyrolytic gas chromatography showed cyclopentadiene was liberated in the thermal process. These overall studies provide strong evidence that loss of a cyclopentadienyl ligand in supported chromium catalysts has a profound effect on overall polymerization behavior.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 2621-2637 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromocene deposited on silica supports of high surface area forms a highly active catalyst for polymerization of ethylene. Polymerization is believed to occur by a coordinated anionic mechanism previously outlined. The catalyst formation step liberates cyclopentadiene and leads to a new divalent chromium species containing a cyclopentadienyl ligand. The catalyst has a very high chain-transfer response to hydrogen which permits facile preparation of a full range of molecular weights. Catalyst activity increases with an increase in silica dehydration temperature, chromium content on silica, and ethylene reaction pressure. The temperature-activity profile is characterized by a maximum near 60°C, presumably caused by a deactivation mechanism involving silica hydroxyl groups. A value of 72 was estimated for the ethylene-propylene reactivity ratio (r1). Linear, highly saturated polymers are normally prepared below 100°C. By contrast with other commercial polyethylenes, the chromocene catalyst produces polyethylenes of relatively narrow molecular weight distribution. Above 100°C, unsaturated, branched polymers or oligomers are formed by a simultaneous polymerization-isomerization process.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 2609-2620 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(triphenylsilyl) chromate is an active catalyst for ethylene polymerization without further treatment or additives. Catalytic activity is markedly increased when the compound is deposited on silica-alumina and is further increased if it is deposited on silica and then treated with an aluminum alkyl. Polymer molecular weight can be controlled by reaction temperature, hydrogen addition, support type, and reducing agent structure to give polymers ranging in melt index from essentially zero to 〉 100. In the supported catalysts the bis(triphenylsilyl) chromate appears to be bound to the support and to undergo a reduction step either by reaction with ethylene or with aluminum alkyl prior to polymerization. The active site is envisioned as chromium alkyl, bound to the support, with propagation occurring by insertion of the monomer into a Cr—C bond. Chain termination is by chain transfer to monomer.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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