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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 103 (1981), S. 1180-1185 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2019-2032 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical composition of a MgCl2-supported, high-mileage catalyst has been determined at every stage of its preparation. Ball milling of MgCl2 with ethyl benzoate (EB) resulted in the incorporation of 95% of the EB present to give MgCl2·EB0.15. A mild reaction with a half-mole equivalent of p-cresol (PC) at 50°C for 1 h resulted in near quantitative retention of p-cresol by the support. The composition is now approximately MgCl2·EB0.15P̌0.5. Addition of an amount of AlEt3 corresponding to half-mole equivalent of p-cresol liberated one mole of ethane per mole of p-cresol, thus signaling quantitative reaction between the two components. The support contains on the average one ethyl group per Al. Further reaction with TiCl4 resulted in the incorporation of titanium of approximately 8, 38, and 54% in the oxidation states of +2, +3, and +4, respectively. The ratio of Al to Ti in the catalyst lies in the range of 0.5-1.0. Only 19% of all the Ti+3 species in the catalyst can be observed by electron paramagnetic resonance (EPR); these are attributable to isolated Ti+3 complexes. The remaining EPR silent Ti+3 species are believed to be bridged to another Ti+3 by Cl ligands. The total Cl content is equal to the sum of 2 × Mg + 3 × Al + 3.5 × Ti. Most of the p-cresol moiety apparently disappeared from the support, leaving much of ethyl benzoate in the catalyst. Activation with AlEt3/methyl-p-toluate complex reduces 90% of the Ti+4 in the catalyst to lower oxidation states. The ester apparently moderates the alkylating power of AlEt3 to avoid excessive formation of divalent titanium sites. There appears to be a constant fraction of 1/4-1/5 of the titanium which is isolated and the remainder is in bridged clusters independent of the oxidation states of titanium.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2461-2476 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electron paramagnetic resonance (EPR) was used to study a MgCl2-supported, high-mileage olefin polymerization catalyst. Anhydrous Toho MgCl2 was the starting material. Treatment with HCl at an elevated temperature, ethyl benzoate by ball-milling, p-cresol, AlEt3, and TiCl4produced a catalyst that contained a single EPR observable Ti+3 species A, which was strongly attached to the catalyst surface, had a D3h symmetry, and no other Ti+3 ion in an immediately adjacent site. Species A constitutes only 20% of all the trivalent titaniums; the remainder is EPR-silent and may be attributed to those Ti+3 ions that have adjacent sites occupied by one or more Ti+3 ions. Activation with preformed AlEt3/methyl-p-toluate complexes produced a single Ti+3 species (C) with rhombic symmetry and displaying 27Al superhyperfin splitting which has attributes for a stereospecific active site. This species is unstable under polymerization conditions and is transformed to another species with axial symmetry and solubilization. Both processes could lead to catalyst deactivation and loss of stereospecificity. Catalysts activated by AlEt3 and methyl-p-toluate separately in various sequential orders produced a multitude of EPR-observable Ti+3 species with varying degrees of motional freedom deemed detrimental to stereospecific polymerization of α-olefins.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 725-736 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fourier transform infrared (FTIR) spectra were obtained for a typical MgCl2-supported, high-mileage catalyst for propylene polymerization. When ball-milling MgCl2 with ethyl benzoate (EB), the latter is incorporated into the support (I) by Lewis acid-base complexation involving both oxygen atoms of the ester. Reaction of (I) with p-cresol (PC) resulted in a material (II) that contains all the characteristic IR bands of PC. The reaction of (II) that contains all the characteristic IR bands of PC. The reaction of (II) with AlEt3 (TEA) resulted in (III) whose spectrum supports the reaction observed by product analysis and NMR spectroscopy. There was no evidence of any reaction between TEA and EB. Further reaction of (III) with an excess of TiCl4 caused substantial removal of the p-cresol moiety as shown by the diminution of its characteristic bands. Finally, activation with 3TEA-1MT (methyl-p-toluate) complexes gave spectra that revealed the presence of MT in the activated catalyst without any visage of p-cresol moiety. The nondestructive FTIR method, however, is not quantitative. Quantitative analysis of the organic components in the support materials (I), (II), and (III) and the catalysts was accomplished by hydrolysis of the inorganic components, extraction with ether, and analysis by gas chromatography. The results are in good agreement with composition deducted from elemental analysis and substantiate the FTIR conclusions.
    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: Polymer Chemistry Edition 20 (1982), S. 2445-2460 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions between AlEt3 and the modifiers, promoters, and coactivators of a typical magnesium-chloride-supported, high-activity propylene polymerization catalyst were studied. Infrared, MS analysis of the gas evolved, and GC-MS of the hydrolysis products for the reaction between AlEt3 and p-cresol showed rapid and quantitative reactions with p-cresol either in the support or solution. The reaction products from AlEt3 and esters were hydrolyzed, acidified, and dehydrated. The resulting carbonyl and olefinic compounds were identified by GC-MS. Proton and carbon nuclear magnetic resonance (NMR) techniques were also used to study these reactions. The expected intermediates were found in the PMR and CMR spectra. The mechanisms of reactions were proposed. The results of this study showed that when AlEt3 and esters are used as coactivators reaction products that can significantly influence the performance of the catalyst are formed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 737-750 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The physical state of the material obtained during the various stages of preparation of a typical MgCl2-supported, high-mileage propylene polymerization catalyst was studied by BET, mercury porosimetry, and x-ray diffraction techniques. The starting MgCl2 and the substance after HCl treatment have negligible BET surface areas. Mercury porosimetry showed that they have large pores with radii 〉 200 nm which are probably crevices between MgCl2 crystallites. The most pronounced physical changes occur during dry porcelain ball milling in the presence of ethyl benzoate. After 60 h or more of ball milling the material had a 5.1-7.3 m2 g-1 BET surface area, twice the pore surface area, and a smaller pore radius than before ball milling and a large reduction in crystallite sizes to almost ultimate dimensions. The crystallites were probably held together by complexation with ethyl benzoate in the form of large agglomerates. Subsequent reactions with p-cresol and triethyl aluminum had minor effects in further reduction of the MgCl2 crystallite size but efficiently brokeup the agglomerates. The final refluxing with TiCl4 increased the BET surface area to 110-150 m2 g-1 but may have increased the crystallite size somewhat due to cocrystallization of TiCl3 and AlCl3 with MgCl2. There may have been only 8-10 crystallites in each catalyst particle. The surface structure of the catalyst resembled those of the classical Ziegler-Natta γ-TiCl3·0.33 AlCl3 catalyst.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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