Macromolecules, Vol.31, No.25, 8720-8724, 1998
High-field C-13 NMR characterization of ethene-1-C-13/propene copolymers prepared with C-s-symmetric ansa-metallocene catalysts: A deeper insight into the regio- and stereoselectivity of syndiotactic propene polymerization
In this paper, we report the results of a 150 MHz C-13 NMR characterization of ethene-1-C-13/propene copolymers at low (<5 mol %) ethene content prepared in the presence of the syndiotactic-selective ansa-metallocene catalyst (Me)(Ph)C(cyclopentadienyl)(9-fluorenyl)ZrCl2 (cocatalyst, MAO). In particular, from the fine structure of the resonances of the ethene-1-C-13 units we conclude that the enantioselectivity of 1,2-propene insertion is substantially lower and the probability of chain back-skip substantially higher after an ethene insertion than after a propene one. Moreover, we find that the regioirregular 2,1-propene units (whose concentration is higher than claimed in the literature) are also substantially stereoirregular.
Keywords:DICHLORIDE METHYLALUMINOXANE CATALYST;C-13-ENRICHED ENDGROUPS;ZIEGLER-NATTA CATALYSTS;ISOTACTIC POLYMERIZATION;ETHYLENEBIS(1-INDENYL)ZIRCONIUM DICHLORIDE;STEREOSPECIFICPOLYMERIZATION;1-ALKENE POLYMERIZATION;MONOMER CONCENTRATION;STEREOERROR FORMATION;ACTIVE-SITE