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Propene polymerization using homogeneous MAO-activated metallocene catalysts : Me2Si(Benz[e]Indenyl)2ZrCl2/MAO vs. Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2/MAO

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Jüngling_239259.pdf
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1995

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Jüngling, Stephan
Mülhaupt, Rolf
Stehling, Udo
Fischer, David
Langhauser, Franz

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Journal of Polymer Science Part A: Polymer Chemistry. 1995, 33(8), pp. 1305-1317. ISSN 0887-624X. eISSN 1099-0518. Available under: doi: 10.1002/pola.1995.080330813

Zusammenfassung

Propene was polymerized at 40°C and 2-bar propene in toluene using methylalumoxane (MAO) activated rac-Me2Si(Benz[e]Indenyl)2ZrCl2 (BI) and rac-Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2 (MBI). Catalyst BI/MAO polymerizes propene with high activity to afford low molecular weight polypropylene, whereas MBI/MAO is less active and produces high molecular weight polypropylene. Variation of reaction conditions such as propene concentration, temperature, concentration of catalyst components, and addition of hydrogen reveals that the lower molecular weight polypropylene produced with BI/MAO results from chain transfer to propene monomer following a 2,1-insertion. A large fraction of both metallocene catalyst systems is deactivated upon 2,1-insertion. Such dormant sites can be reactivated by H2-addition, which affords active metallocene hydrides. This effect of H2-addition is reflected by a decreasing content of head-to-head enchainment and the formation of polypropylene with n-butyl end groups. Both catalysts show a strong dependence of activity on propene concentration that indicates a formal reaction order of 1.7 with respect to propene. MBI/MAO shows a much higher dependence of the activity on temperature than BI/MAO. At elevated temperatures, MBI/MAO polymerizes propene faster than BI/MAO.

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540 Chemie

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Propene, polymerization, zirconocene, methylalumoxane, chain transfer, end groups, hydrogen, 2, 1-insertion

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ISO 690JÜNGLING, Stephan, Rolf MÜLHAUPT, Udo STEHLING, Hans-Herbert BRINTZINGER, David FISCHER, Franz LANGHAUSER, 1995. Propene polymerization using homogeneous MAO-activated metallocene catalysts : Me2Si(Benz[e]Indenyl)2ZrCl2/MAO vs. Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2/MAO. In: Journal of Polymer Science Part A: Polymer Chemistry. 1995, 33(8), pp. 1305-1317. ISSN 0887-624X. eISSN 1099-0518. Available under: doi: 10.1002/pola.1995.080330813
BibTex
@article{Jungling1995Prope-23925,
  year={1995},
  doi={10.1002/pola.1995.080330813},
  title={Propene polymerization using homogeneous MAO-activated metallocene catalysts : Me<sub>2</sub>Si(Benz[e]Indenyl)<sub>2</sub>ZrCl<sub>2</sub>/MAO vs. Me<sub>2</sub>Si(2-Me-Benz[e]Indenyl)<sub>2</sub>ZrCl<sub>2</sub>/MAO},
  number={8},
  volume={33},
  issn={0887-624X},
  journal={Journal of Polymer Science Part A: Polymer Chemistry},
  pages={1305--1317},
  author={Jüngling, Stephan and Mülhaupt, Rolf and Stehling, Udo and Brintzinger, Hans-Herbert and Fischer, David and Langhauser, Franz}
}
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