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28
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3643067691
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note
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Some of the polymer blends prepared from combinations of 1-rac and 1-meso were fractionated below the boiling point of hexanes using a Soxhlet extraction apparatus but gave results identical to the fractionations run at the boiling point.
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29
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0021517472
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Chujo's concurrent model assumes that two sites of differing stereospecificity undergo polymerization simultaneously to yield a polymer blend. Stereoblock polypropylene is a limiting case for this model, and error in the calculated isotactic weight fraction may be introduced due to the interfacial region between the isotactic and atactic blocks. The Chujo method and a method which simulates the pentad distribution of the stereoblock material calculate similar isotactic weight fractions (0.27 vs 0.3), indicating that the Chujo method gives a good approximation of the fraction of isotactic polymer contained in the stereoblock polypropylene. See: Inoue, Y.; Itabashi, I.; Chujo, R.; Doi, Y. Polymer 1984, 25, 1640-1644. Bruce, M. D.; Waymouth, R. M. Macromolecules 1998, 31, 2707-2715.
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Chujo's concurrent model assumes that two sites of differing stereospecificity undergo polymerization simultaneously to yield a polymer blend. Stereoblock polypropylene is a limiting case for this model, and error in the calculated isotactic weight fraction may be introduced due to the interfacial region between the isotactic and atactic blocks. The Chujo method and a method which simulates the pentad distribution of the stereoblock material calculate similar isotactic weight fractions (0.27 vs 0.3), indicating that the Chujo method gives a good approximation of the fraction of isotactic polymer contained in the stereoblock polypropylene. See: Inoue, Y.; Itabashi, I.; Chujo, R.; Doi, Y. Polymer 1984, 25, 1640-1644. Bruce, M. D.; Waymouth, R. M. Macromolecules 1998, 31, 2707-2715.
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A large twist angle (60°) has also been observed for silyl bridged metallocenes containing a 2-p-tolylindenyl ligand. See: Yoon, S. C.; Han, T. K.; Woo, B. W.; Song, H.; Woo, S. I.; Park, J. T. J. Organomet. Chem. 1997, 534, 81-87. Yoon, S. C.; Park, J.-W.; Jung, H. S.; Song, H.; Park, J. T.; Woo, S. I. J. Organomet. Chem. 1998, 559, 149.
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This trend in reactivity is in contrast to that observed for analogous unbridged systems. Bis(2-phenylindenyl)zirconium dichloride (2) is more productive than bisindenylzirconium dichloride in both ethylene and propylene polymerizations. Some have attributed the higher productivity of 2 to conjugation of the phenyl ring with the indenyl framework in effect destabilizing the metal ligand bond and thereby increasing the reactivity of the metal center. See: Bravaya, N. M.; Dzhabieva, Z. M.; Maryin, V. P.; Strelets, V. V. Polimery 1997, 42, 591-594. Bruce, M. D.; Waymouth, R. M. Ph.D. Thesis, Stanford University, Stanford, CA, 1997.
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This trend in reactivity is in contrast to that observed for analogous unbridged systems. Bis(2-phenylindenyl)zirconium dichloride (2) is more productive than bisindenylzirconium dichloride in both ethylene and propylene polymerizations. Some have attributed the higher productivity of 2 to conjugation of the phenyl ring with the indenyl framework in effect destabilizing the metal ligand bond and thereby increasing the reactivity of the metal center. See: Bravaya, N. M.; Dzhabieva, Z. M.; Maryin, V. P.; Strelets, V. V. Polimery 1997, 42, 591-594. Bruce, M. D.; Waymouth, R. M. Ph.D. Thesis, Stanford University, Stanford, CA, 1997.
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3643057115
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This value is limited by the accuracy of NMR integration for both the polymers and catalyst mixtures
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Some recent reports have claimed elastomeric properties for reactor blends derived from isospecific and aspecific metallocenes. See: Canich, J. A. M.; Yang, H. W.; Licciardi, G. F. (Exxon) U. S. Pat. 5516848 A, 960514.
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Caution should be exercised when running polymerizations in liquid propylene. An exotherm initiated by a particularly productive metallocene (i.e.: 3-rac) can cause a dangerous increase in pressure in the reaction vessel
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Caution should be exercised when running polymerizations in liquid propylene. An exotherm initiated by a particularly productive metallocene (i.e.: 3-rac) can cause a dangerous increase in pressure in the reaction vessel.
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