Macromolecules, Vol.32, No.25, 8283-8290, 1999
Regioirregular propene insertion in polypropenes synthesized with unbridged bis(2-aryl)indenyl zirconium dichloride catalysts: Implications on activity
Catalysts of the type bis(2-(3,5-R2C6H3)indenyl)zirconium dichloride/MAO (2, R = H; 3, R = CF3) were investigated for regioregularity of monomer insertion in bulk propene polymerization and compared to the isospecific catalyst rac-(ethene)bis(indenyl)zirconium dichloride/MAO (1). The amount of regioirregular propene insertions were in the range of 0.1-0.5 mol % and followed the trend 2 < 3 < 1. Comparison of polymerizations in the presence and absence of hydrogen revealed a 4-10-fold increase in productivity for catalysts 2 and 3 in the presence of hydrogen but only a slight increase in productivity with 1. For catalysts 2 and 3, only 2,1-erythro internal regioerrors were observed, whereas 1 produced both 2,1-erythro and 2,1-threo misinsertions. Evidence for ethene insertion following a 2,1-regioerror was obtained by copolymerization of (C2H4)-C-13 with propene using catalyst 3. The correlation between number of 2,1-misinsertions and catalyst activity is discussed.
Keywords:ACTIVATED METALLOCENE CATALYSTS;ZIEGLER-NATTA OLIGOMERIZATION;ELASTOMERIC POLYPROPYLENE;POLYMERIZATION;STEREOSPECIFICITY;HYDROOLIGOMERIZATION;STEREOREGULARITY;REGIOREGULARITY;MICROSTRUCTURE;ZIRCONOCENES