Mechanisms of stereocontrol for doubly silylene-bridged C{sub s}- and C{sub 1}-symmetric zirconocene catalysts for propylene polymerization. Synthesis and molecular structure of Li{sub 2}[(1,2-Me{sub 2}Si){sub 2}{l{underscore}brace}C{sub 5}H{sub 2}-4-(1R,2S,5R-methyl){r{underscore}brace}{l{underscore}brace}C{sub 5}H-3,5-(CHMe{sub 2}){r{underscore}brace}]{center{underscore}dot}3THF[(1,2-Me{sub 2}Si){sub 2}{l{underscore}brace}{eta}{sup 5}-C{sub 5}H{sub 2}-4-(1R,2S,5R-menthyl){r{underscore}brace}{l{underscore}brace}{eta}{sup 5}-C{sub 5}H-3,5-(CHMe{sub 2}){sub 2}{r{underscore}brace}]ZrCl{sub 2}

Journal Article · Wed Jan 27 04:00:00 EST 1999 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja982868j· OSTI ID:20014089

Veghini, D; Henling, L M; Burkhardt, T J; Bercaw, J E

Doubly [SiMe{sub 2}]-bridged metallocenes (1,2-SiMe{sub 2}){sub 2}{l{underscore}brace}{eta}{sup 5}-C{sub 5}H{sub 2}-4-R{r{underscore}brace}{l{underscore}brace}{eta}{sup 5}-C{sub 5}H-3,5-(CHMe{sub 2}){sup 2}{r{underscore}brace}ZrCl{sub 2} (R = H (1a), CHMe{sub 2} (1b), SiMe{sub 3} (1c), CHMe(CMe{sub 3}) (1d), (+)-menthyl (1e)), when activated by methylaluminoxane (MAO), catalyze propylene polymerization with high activities. The preparations and X-ray structures of the dilithio salt of an enantiopure, doubly silylene-bridged bis(cyclopentadienyl)ligand, Li{sub 2}[(1,2-Me{sub 2}Si){sub 2}-{l{underscore}brace}C{sub 5}H{sub 2}-4-(1R,2S,5R-menthyl){r{underscore}brace}{l{underscore}brace}(C{sub 5}H-3,5-(CHMe{sub 2}){sub 2}){r{underscore}brace}]{center{underscore}dot}3THF, as well as the corresponding zircononcene dichloride, [(1,2-Me{sub 2}Si){sub 2}{l{underscore}brace}{eta}{sup 5}-C{sub 5}H{sub 2}-4-(1R,2S,5R-menthyl){r{underscore}brace}{l{underscore}brace}{eta}{sup 5}-C{sub 5}H-3,5-(CHMe{sub 2}){sub 2}{r{underscore}brace}]ZrCl{sub 2}(1e), are reported. The C{sub s}-symmetric systems 1a-c are highly regiospecific and syndiospecific (> 99.5%) in neat propylene. At lower propylene concentrations, polymers with lower molecular weights and tacticity (mostly m-type stereoerrors) are obtained. The microstructures of polymers produced under differing reaction conditions are consistent with stereocontrol dominated by a site epimerization process, an inversion of configuration at zirconium resulting from the polymer chain swinging from one side of the metallocene wedge to the other without monomer insertion. The relative importance of chain epimerization (at the {beta} carbon) has been established by parallel polymerization of 2-d{sub 1}-propylene and d{sub 0}-propylene with 1b/MAO at low propylene concentrations. The C{sub 1}-symmetric systems 1d,e/MAO display an unusual dependence of stereospecificity on propylene concentration, switching from isospecific to syndiospecific with increasing propylene pressure, consistent with a competitive unimolecular site epimerization process and a bimolecular chain propagation. The microstructures of the polypropylenes produced by 1d/MAO and 1e/MAO with [r] {approx} 50% resemble the hemiisotactic microstructure produced by Me{sub 2}C({eta}{sup 5}-C{sub 5}H{sub 3}-3-Me)({eta}{sup 5}-C{sub 13}H{sub 8})ZrCl{sub 2} (2b)/MAO. Contrastingly, the hemiisotactic polypropylene microstructure obtained with 2b/MAO is found to be maintained at all propylene concentrations examined.

• Research Organization: California Inst. of Tech., Pasadena, CA (US)
• Sponsoring Organization: US Department of Energy
• DOE Contract Number: FG03-85ER13431
• OSTI ID: 20014089
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 3 Vol. 121; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
MOLECULAR STRUCTURE
POLYMERIZATION
PROPYLENE
SILANES
SYNTHESIS
ZIRCONIUM COMPOUNDS