PROPYLENE POLYMERIZATION WITH CHIRAL AND ACHIRAL UNBRIDGED 2-ARYLINDENE METALLOCENES

Citation
R. Kravchenko et al., PROPYLENE POLYMERIZATION WITH CHIRAL AND ACHIRAL UNBRIDGED 2-ARYLINDENE METALLOCENES, Organometallics, 16(16), 1997, pp. 3635-3639
Citations number
36
Categorie Soggetti
Chemistry Inorganic & Nuclear","Chemistry Inorganic & Nuclear
Journal title
ISSN journal
02767333
Volume
16
Issue
16
Year of publication
1997
Pages
3635 - 3639
Database
ISI
SICI code
0276-7333(1997)16:16<3635:PPWCAA>2.0.ZU;2-6
Abstract
Unbridged 2-arylindenyl metallocene complexes, such as bis(2-phenylind enyl)zirconium dichloride, in the presence of methyaluminoxane (MAO) a re catalyst precursors for the synthesis of elastomeric polypropylenes . The effects of 1-methyl substitution on the polymerization behavior of these unbridged 2-arylindene complexes have been studied. The react ion of the lithium salt of 1-methyl-2-phenylindene with ZrCl4 leads to the formation of two diastereomers of bis(1-methyl-2-phenylindenyl)zi rconium dichloride: rac- and meso-(1-Me-2-PhInd)(2)ZrCl2. The two isom ers have been separated by fractional crystallization and identified b y X-ray crystallography. X-ray crystallographic analysis reveals that the dihedral angles between the planes of the phenyl and the indenyl r ings have significantly increased upon 1-methyl substitution (28-34 de grees compared to 10-12 degrees for unsubstituted (2-PhInd)(2)ZrCl2), which suggests strong steric repulsion between the 1-methyl and 2-phen yl groups. In ethylene polymerization, the productivity of the catalys t derived from the meso-isomer is similar to that of the catalyst deri ved from (2-PhInd)(2)ZrCl2; higher productivity is observed for the ca talyst derived from the rac-isomer. In polymerization of propylene, bo th substituted catalysts have a significantly lower productivity than the catalyst derived from unsubstituted (2-PhInd)(2)ZrCl2 and generate amorphous polypropylene with a low molecular weight and isotacticity.