Journal of Polymer Science Part A: Polymer Chemistry, Vol.33, No.8, 1305-1317, 1995
Propene Polymerization Using Homogeneous Mao-Activated Metallocene Catalysts - Me(2)Si(Benz(E)Indenyl)(2)Zrcl2/Mao vs Me(2)Si(2-Me-Benz(E)Indenyl)(2)Zrcl2/Mao
Propene was polymerized at 40 degrees C and 2-bar propene in toluene using methylalumoxane (MAO) activated rac-Me(2)Si(Benz[e]Indenyl)(2)Zr Cl-2 (BI) and rac-Me(2)Si(2-Me-Benz[e]Indenyl)(2)ZrCl2 (MBI). Catalyst BI/MAO polymerizes propene with high activity to afford low molecular weight polypropylene, whereas MBI/MAO is less active and produces high molecular weight polypropylene. Variation of reaction conditions such as propene concentration, temperature, concentration of catalyst components, and addition of hydrogen reveals that the lower molecular weight polypropylene produced with BI/MAO results from chain transfer to propene monomer following a 2,1-insertion. A large fraction of both metallocene catalyst systems is deactivated upon 2,1-insertion. Such dormant sites can be reactivated by H-2-addition, which affords active metallocene hydrides. This effect of H, addition is reflected by a decreasing content of head-to-head enchainment and the formation of polypropylene with n-butyl end groups. Both catalysts show a strong dependence of activity on propene concentration that indicates a formal reaction order of 1.7 with respect to propene. MBI/MAO shows a much higher dependence of the activity on temperature than BI/MAO. At elevated temperatures, MBI/MAO polymerizes propene faster than BI/ MAO.
Keywords:ZIEGLER-NATTA OLIGOMERIZATION;STEREOCHEMICAL CONTROL;OLEFIN POLYMERIZATION;ZIRCONOCENE CATALYSTS;MOLECULAR-WEIGHT;ETHYLENE;DERIVATIVES;HYDROOLIGOMERIZATION;COPOLYMERIZATION;MICROSTRUCTURE