Browsing by Subject "Metallocene"
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Item Design and synthesis of new C1 and C2-symmetric ansa-metallocene catalysts for isotactic-polypropylene formation(Texas A&M University, 2006-04-12) Al-Bahily, Khalid ASeveral ansa C1-symmetric cyclopentadienyl-fluorenyl metallocenes based on zirconium have been prepared with different substituents at position 3 on the cyclopentadienyl ring. Isotactic polypropylene production from these systems depends highly on the size of these substituents. Therefore, large groups such as 1-methyl-4-tbutylcyclohexyl (metallocene 6), 1-methyl-cyclohexyl (metallocene 7), 1,3,3,5- tetramethylcyclohexyl (metallocene 8), and 2,3,4-trimethyl-3-pentyl (metallocene 9) have been investigated. In combination with methylaluminoxane (MAO), they showed good activity and produced high molecular weight of isotactic polypropylene. In terms of the tacticity of the polymers, metallocene 6 made the best isotactic polypropylene with ~88% mmmm pentad content. Also, it has been found that if the size of this substituent is large as in 2,3,4-trimethyl-3-pentyl (metallocene 9), then it will block the polymerization active site which will deactivate the metallocene. New synthetic pathways for the synthesis of cyclopentadienyl-fluorenyl metallocenes based on titanium have been achieved. Anchoring these types of ligands onto titanium by following the conventional method of using TiCl4 in the metallation step has failed for the production of Me2C(3-(diphenylmethyl)-C5H3)(C13H8)TiCl2 (metallocene 12), Ph2C(C5H4)(C13H8)TiCl2 (metallocene 14), and Ph2C(C5H4)(C13H8)TiMe2 (metallocene 15); this is possibly due to the high reactivity of TiCl4. Therefore, TiCl4??2THF has been prepared and used in that step to produce these new titanocenes with good yields. A new ansa-C2-symmetric substituted bis-indenyl metallocene for isotactic polypropylene production has been successfully prepared. It is known that ansa-C2- symmetric metallocenes are good catalysts for isotactic polypropylene production, but in general, their synthesis suffers from the production of the meso Cs-stereoisomer of these catalysts, which generally produces only atactic polypropylene. Therefore, the meso stereoisomers must be removed and this is considered a loss of the material that increases the cost of the catalysts. Addition of bulky substituents on the indenyl groups as in Me2Si(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl)2ZrCl2 (metallocene 5) has prevented the meso stereoisomer production. 5/MAO produces isotactic polypropylene with up to ~80% mmmm pentad content.Item Structure-activity relationships in olefin polymerization catalysts(2009-05-15) Price, Craig JustinThe thermodynamic parameters associated with the copolymerization of ethylene and carbon dioxide were calculated using bond dissociation energies, the Benson additivity method and density functional theory calculations (DFT). In all cases, the formation of an alternation copolymer was found to be endergonic at any reasonable polymerization temperatures (the ceiling temperature is calculated to be -159 ?C). However, the polymerization was calculated to be exergonic at room temperature, as long as the incorporation of CO2 is less than 29.7 mol%. Experiments failed to provide evidence of any CO2 incorporation, despite previously published reports claiming up to 30 mol%. Octamethyloctahydrodibenzofluorenyl (Oct) has profound steric consequences when incorporated into metallocene olefin polymerization catalysts ? including increased catalytic activity and stereoselectivity. However, the electronic effect of the ligand?s four electron-donating tertiary alkyl groups is less understood. NMR and DFT calculations were used to study the electronic nature of the Oct moiety ? both as a part of ansa-metallocene pre-catalysts and as an independent molecule. The results show that Oct is more electron rich than other cyclopentadienyl analogues and that the electronics of the ligand are readily conveyed to the metal center. Upon activation, the steric bulk of the Oct moiety dominates the immediate environment around the metal center. Evidence is presented that supports previous theories about Oct?s ability to influence the counteranion distance, thereby increasing the catalytic activity. In addition, excess trimethyl aluminum (TMA) is known to be detrimental to catalytic activity and results uphold this belief ? although the magnitude of the effect varies depending on the metallocene being studied. However, UV-Vis data do not support the theory that TMA binds to the catalytically-active metal center, thereby decreasing the catalytic activity; but does not offer an alternate mechanism.