Polypropylene and Ethylene−Propylene Copolymer Reactor Alloys Prepared by Metallocene/Ziegler−Natta Hybrid Catalyst

Polypropylene/ethylene−propylene rubber (PP/EPR) reactor alloys were prepared with a metallocene/Ziegler−Natta hybrid catalyst system (rac-Et(Ind)2ZrCl2/TiCl4/MgCl2) using a process composed of three stages: propylene homopolymerization, metallocene activation, and ethylene−propylene copolymerization. A series of alloy samples were produced and characterized at various copolymerization conditions by varying the methylaluminoxane (MAO)/Zr ratio and monomer composition. It was shown that the metallocene/Ziegler−Natta hybrid system exhibited the features of both metallocene and Ziegler−Natta catalysts during copolymerization. The hybrid catalyst had better ability in incorporating α-olefin than the Ziegler−Natta catalyst owing to the action of metallocene active sites. DSC and IR analyses suggested that EPR in the alloys became random with increased MAO/Zr ratio. In addition, reducing the ethylene content in the feed decreased the activity and promoted the production of random copolymers. An operation window of reaction conditions was identified for the preparation of well-dispersed spherical PP/EPR reactor alloy particles containing up to about 40 wt % EPR.