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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 243-249 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Detailed studies were made of the course of the terpolymerization of ethylene, propylene, and dicyclopentadiene to form unsaturated elastomers. All the dicyclopentadiene was added at the start of a polymerization, but the monoolefins were added continuously throughout the run. Under these conditions, unsaturation of the initial polymer is fairly high but decreases steadily as the reaction progresses. From analyses of the initial samples from each run, the catalyst of VCl4 (with Al2Et3Cl3 cocatalyst), with heptane as the polymerization solvent, was most efficient for introducing unsaturation into terpolymer. This system also produces gel in the terpolymer in the latter stages of reaction, however. Catalysts of VCl4, VOCl3, or V(C5H7O2)3, with Al2Et3Cl3 cocatalyst, in benzene solvent gave terpolymers of quite similar unsaturations. With all systems, terpolymer yield increases very rapidly in the first few minutes of reaction, then very slowly for the remainder of the 30-min. reaction time, reflecting the rapid loss of activity of the vanadium catalysts. Molecular weight growth of the terpolymer prepared in heptane was extremely rapid, reaching a high value in a few minutes. When prepared in benzene, the terpolymers showed a steady increase in molecular weight throughout the reaction but reached only a moderate final value (as expressed by inherent viscosity).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1323-1325 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Catalysts were prepared from titanium tetrachloride and tri-n-propylaluminum or tri-n-propylaluminum anisole at [Al]/[Ti] molar ratios of 0.20-1.10. They were aged and filtered, and the solid and liquid portions were analyzed for aluminum, titanium, chlorine, and certain organic constituents. The analyses indicate that the solid of the nonetherate catalyst is predominantly TiCl3, some AlCl3 or aluminum alkyl chlorides being included. Only at [Al]/[Ti] = 1.10 was any alkyl group found in the solid. The same general results were found for the etherate catalyst, but the solid had a somewhat lower [Cl]/[Ti] ratio, indicating greater reduction or alkylation, or both, of the titanium species than in the nonetherate catalyst. The solid also contained some anisole at the higher [Al]/[Ti] ratios. The results lend general support to proposed reactions for the catalyst formation. The main differences in the etherate catalysts relative to the non-etherate system, particularly at the higher [Al]/[Ti] ratios, are the apparently greater reduction or alkylation of the titanium in the solids, the presence of anisole in the liquid and solid portions, and the presence of phenol in the liquid portion. The phenol presumably comes from cleavage of the anisole during the catalyst formation. Not all of the anisole has been accounted for in a materials balance, nor has all of the chlorine in the etherate catalysts. No propyl or isopropyl chloride was found in the catalysts; there is no significant amount of polypropylene in any of the catalyst solids. Hence the fate of the alkyl groups remains undetermined at present.
    Additional Material: 9 Tab.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 251-256 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Terpolymerizations of ethylene, propylene, and dicyclopentadiene were carried out in which the dicyclopentadiene was added to the reaction system in two equal portions at the beginning and midpoint of each run, while the monoolefins were added continuously. In the resultant elastomers, unsaturation remains much more constant throughout the course of the polymerization than for terpolymers obtained when all dicyclopentadiene is added at the start of the reaction. Yield and molecular weight of the terpolymers produced by either technique are quite comparable, however. With VCl4 catalyst (with Al2Et3Cl3 cocatalyst) in heptane solvent, the two-step addition of the diene gave terpolymers with little gel, in contrast to the high gel in terpolymers formed with the single initial addition of the diene. This system also produced terpolymer with the highest final unsaturation and molecular weight. Catalysts of VCl4, VOCl3, or V(C5H7O2)3 in benzene gave terpolymers of moderate unsaturations and molecular weights.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1203-1208 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vanadium trisacetylacetonate [V(C5H7O2)3] and vanadyl bisacetylacetonate [VO-(C5H7O2)2] were found to be satisfactory catalysts (with Al2Et3Cl3 cocatalyst) for the terpolymerization of ethylene, propylene, and dicyclopentadiene to unsaturated, sulfurcurable elastomers. Polymerization solvents of heptane or benzene were used. Best yields of terpolymers were obtained in benzene. Terpolymers with unsaturations of greater than ≃0.20 mole C=C/kg. can be cured with a sulfur-based vulcanzing recipe. Both acetylacetonates produced terpolymers, in benzene, with practically equivalent properties. They also appeared to be nearly equal to corresponding terpolymers made with catalysts of VOCl3 or VCl4.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 391-394 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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