Journal of Polymer Science Part A: Polymer Chemistry, Vol.34, No.14, 2945-2953, 1996
Syndioselective Propylene Polymerizations by Ansa-Zirconocenium Catalyst
The effect of reaction conditions, including catalyst concentration, temperature, and immobilization on support, have been investigated for syndioselective propylene polymerization by the "bare" zirconocenium ion generated from 1,1-diphenyl-methylidene(1-eta(5)-cyclopentadienyl) (9-eta(5)-fluorenyl)zirconium-dichloride precursor (2). Neither variation of the catalyst concentration nor immobilization of 2 on silica support affect the syndiospecificity of polymerization. The stereoregularity of the syndiotactic polypropylene, as judged from the melting transition temperature and homosteric r-pentad population by C-13-NMR, were found to be proportional to polymer molecular weight. These behaviors are compared with a typical isoselective catalyst ethylenebis(4,5,6,7-tetrahydroindenyl) Zr precursor (4). They are in close resemblance in the case of the S-enantiomeric complex of 4, but the racemic mixture of 4 is markedly inferior. The origins of stereo- and regio-errors are discussed.
Keywords:HOMOGENEOUS OLEFIN POLYMERIZATION;PROPENE POLYMERIZATION;METALLOCENE DERIVATIVES;ISOSPECIFIC POLYMERIZATION;ISOTACTIC POLYMERIZATION;1-ALKENE POLYMERIZATION;STEREOCHEMICAL CONTROL;MONOMER CONCENTRATION;BRIDGED ZIRCONOCENE;ABINITIO MO