The Use of Functionalized Zirconocenes as Precursors to Silica-Supported Zirconocene Olefin Polymerization Catalysts
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Deck and coworkers previously showed that Me3Si substituents adjacent to group 4 metallocene dichlorides (M = Ti, Zr, Hf) are converted to corresponding BrMe2Si groups using BBr3, and that these BrMe2Si substituents are highly reactive to nucleophilic reagents such as water. The high reactivity of the Si-Br bonds suggested that these substituents could react with hydroxyl groups on the surface of partially dehydroxylated silica, forming covalently immobilized metallocene catalysts. This dissertation concerns the synthesis of electrophile-functionalized zirconocene dihalide complexes and the use of functionalized zirconocene dihalides as precursors to silica-supported metallocene olefin polymerization catalysts. Our first objective was to extend the metallocene "functionalization" chemistry to obtain substituents bearing more than one electrophilic bond. The reactivities of Me3Sn and Ph2MeSi substituents were explored in detail. (Me3Sn)2C5H4 combined with CpZrCl3 in toluene to afford (h5-Me3Sn-C5H4)CpZrCl2 (A). Reactions of A with electrophiles (E-X = Cl2B-Cl, I-Cl, and I-I) afforded (ï ¨5-XMe2Sn-C5H4)CpZrCl2 (and E-Me) cleanly. The reaction of A with BBr3 afforded either (ï ¨5-BrMe2Sn-C5H4)CpZrBr2 (25 ï °C, 10 min) or (ï ¨5-Br2MeSn-C5H4)CpZrBr2 (25 ï °C, 15 h). Ph2MeSi-C5H4Li combined with ZrCl4â ¢2THF to afford (h5-Ph2MeSi-C5H4)2ZrCl2 (B). The reaction of B with BCl3 led to incomplete cleavage of the Ph-Si bonds, however treatment of B with BBr3 afforded (h5-Br2MeSi-C5H4)2ZrBr2 (C) efficiently. The Sn-X bonds of the stannylated metallocenes were however relatively unreactive toward water and were excluded as candidates precursors for supported metallocene catalysts. X-ray crystal structures of (h5-ClMe2Sn-C5H4)CpZrCl2â ¢Â½toluene, (h5-Br2MeSn-C5H4)CpZrBr2â ¢THF, B, and C were obtained. The functionalized metallocene C reacts with water to afford an oligosiloxane-supported zirconocene dibromide. Combinations of solution 1H NMR, solid state CPMAS 13C NMR, and solid state CPMAS 29Si NMR spectroscopy suggested a stereoregular structure in which the metallocene units have local Cs (meso) symmetry. Although only sparingly soluble, the oligomeric substance showed activity for homogeneous ethylene polymerization (toluene solution, MAO cocatalyst, Al:Zr = 5000, 50 ï °C) similar to Cp2ZrCl2. Supported metallocene olefin polymerization catalysts were prepared by combining a functionalized metallocene precursor (Cp2ZrBr2 bearing either BrMe2Si or Br2MeSi groups) and partially dehydroxylated silica. Ethylene polymerization activity of the resulting catalysts was examined as a function of the precursor structure (number of reactive "tethering" groups, one vs. two Si-Br bonds per tethering group) and the immobilization conditions (time, temperature, presence or absence of NEt3 promoter). The activities of the immobilized zirconocene catalysts decreased and the stabilities increased with increasing number of tethers. The immobilized catalyst prepared from (ï ¨5-Br2MeSi-C5H4)2ZrBr2, which is assumed to form two "double-tethers" to silica, was significantly more active than the catalyst prepared from [ï ¨5-1,3-(BrMe2Si)2C5H3]2ZrBr2, which is assumed to form four "single-tethers" to silica. Catalyst leaching was observed in all the immobilized zirconocene catalysts. The use of NEt3 in the immobilization reaction enabled more metallocene to be supported, but the resulting activity was lower. The dissertation also includes model studies on the immobilization reaction and the stability of the Si-O-Si bonds. The reaction of C with tBuMe2SiOH results in the formation of Si-O-Si bonds; addition of NEt3 results in further reaction to afford Si-O-Zr bonds. The reaction of Reaction of Me3Si-O-SiMe3 with MAO showed that Si-O-Si bonds can be cleaved under the conditions of our polymerization reactions.
- Doctoral Dissertations