Origin of the formation of the 4‐butenyl end group in zirconocene‐catalyzed propylene polymerization

It has been proposed that the 4-butenyl end group in polypropylene is formed by isomerization of the 2-butenyl end group. Prior experimental evidence has shown that the isomerization is not produced thermally or upon an acidic treatment during the workup or analysis of the polymer. We postulate that the production of the 4-butenyl end group by isomerization might be catalyzed by a zirconocene hydride complex that forms during the β-hydride elimination reaction. The isomerization of a preformed olefinic-end-group isotactic polypropylene with a well-known transition-metal hydride shows the disappearance of the 2-butenyl end group concomitant with the appearance of the 4-butenyl end group.