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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 28 (1958), S. 387-394 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low and atmospheric pressure polymerizations of ethylene using catalysts prepared from n-butyl lithium or isoamyl lithium and titanium tetrachloride were studied. The efficiency of the catalyst depended on the molecular ratio of the alkyl lithium to titanium tetrachloride. Optimum molecular ratio for the n-butyl lithium-titanium tetrachloride was found to be between 2.15-2.47 with a sharp drop between 2.15-1.49; for the isoamyl lithium the optimum was between 2.5-4.3. Within the examined interval (of atmospheric pressure to a pressure of 60-70 lb./sq. in.) higher pressure caused an increase in the yield of polyethylene. No pronounced effect in polymerization was found in the temperature interval of -10-55°. The catalyst is stable for a few days if kept refrigerated. Petroleum ether, b.p. 40-80°, was the best solvent both for the preparation of the catalyst and for the polymerization. Ligroin, toluene, and especially ether interfered with the polymerization. The polyethylenes obtained melted between 125-135°.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 33 (1958), S. 141-152 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low pressure polymerization of ethylene with the use of catalysts prepared from various sodium alkyls and titanium tetrachloride was studied. Catalysts prepared from amylsodium were very active over a wide range of molar ratios of amylsodium to titanium tetrachloride (2-50); the activity decreased sharply with lower molar ratios. Rate of polymerization was found to decrease sharply, probably as a result of fusing of polyethylene particles to the catalyst surface during polymerization. Up to a pressure of about three atmospheres, the polymerization gave better yields with increase in pressure, but no increase in rate was observed on using higher pressures. Yields increased also with lowering of temperature; 0°C. gave the best yields. Molecular weight determinations showed that the polyethylenes produced had high molecular weights which did not vary over a wide range. With butylsodium, catalysts similar to those with amylsodium were formed; they showed a smaller optimum range (5-9) of molar ratios of alkyl sodium to titanium tetrachloride. Catalysts prepared from phenylsodium were much weaker, and the optimum molar ratio of phenylsodium to titanium tetrachloride, contrary to the other sodium alkyls, was found to lie at much lower molar ratios of alkyl sodium to titanium tetrachloride. Polymerizations were, in the case of phenylsodium, accompanied by an induction effect. Preliminary studies on the preparation of catalysts for the low pressure polymerization of ethylene in the presence of cyclopentadienylsodium and titanium tetrachloride were as yet not successful.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 39 (1959), S. 347-356 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low pressure polymerization of ethylene by use of catalysts prepared from either butyl or amyl potassium, or the reaction product of potassium with chlorobenzene and titanium tetrachloride was studied. The efficiency of the catalysts depended on the molar ratio of the potassium alkyl to titanium tetrachloride but was in every case considerably lower than that of the corresponding lithium or sodium alkyl containing catalysts. Optimum molar ratios of the butyl potassium-titanium tetrachloride catalysts were between 2.8 to 6.1 with sharp drops on both sides of the optimum; for the amyl potassium between 1.1 to 3.7. The reaction product of potassium with chlorobenzene yielded much weaker catalysts with titanium tetrachloride, and the properties of the polymers obtained were different. The physical properties of the polyethylenes obtained, as determined from x-ray diffraction diagrams, infrared spectra, and from melting points, showed similarity to those obtained with the lower alkali metal catalysts. The lower activity of the potassium catalysts may be related to the large ionic radius of the potassium, which influences the properties of the catalyst complex formed with titanium tetrachloride. Propylene did not undergo polymerization with the potassium alkyl containing catalysts at low pressure.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 40 (1959), S. 149-158 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low pressure polymerization of propylene was investigated using catalysts prepared from alkali metal alkyls and titanium tetrachloride. In all cases the efficiency of the catalysts depended on the molecular ratio of the metal alkyl to the titanium tetrachloride. In general the polymerization conditions were similar to those for ethylene although the propylene polymerized much more slowly. With n-butyllithium-titanium tetrachloride, optimum molecular ratios were found between 1.8-2.5, with sharp drops on both sides. With amylsodium-titanium tetrachloride the optimum extended over a wide range (5.7-15), the activity decreasing sharply with lower molecular ratios. The catalysts prepared from sodium alkyls were more active than those prepared from lithium alkyls. Increasing yield was obtained on lowering the concentration of the catalyst. Up to a pressure of about 3 atmospheres, increase in the rate of polymerization was observed with increase in pressure; above this no influence of the pressure was observed. Isotactic polymers were isolated from the polymerization products by successive fractionation of the crude polymers in acetone, ether, and isooctane which dissolved the atactic polymers. With butyllithium-titanium tetrachloride catalysts, at and above optimum ratios, the isotactic fractions were about 60%. At lower ratios there was a great increase in atactic polymers. With amylsodium-titanium tetrachloride catalysts the isotactic fractions were about 70%. Phenylsodium-titanium tetrachloride catalysts were found to be very weak in the polymerization of propylene.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0095-9898
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Additional Material: 4 Ill.
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