Preparation of functionalized montmorillonites and their application in supported zirconocene catalysts for ethylene polymerization

Ethylene polymerization was carried out with zirconocene catalysts supported on montmorillonite (or functionalized montmorillonite). The functionalized montmorillonite was from simple ion exchange of [CH3O2CCH2NH3]+(MeGlyH+) ions with interlamellar cations of layered montmorillonites. The functionalized montmorillonites [high‐purity montmorillonite (MMT)‐MeGlyH+] had larger interlayer spacing (12.69 Å) than montmorillonites without treatment (9.65 Å). The zirconocene catalyst system [Cp2ZrCl2/methylaluminoxane (MAO)/MMT‐MeGlyH+] had much higher Zr loading and higher activities than those of other zirconocene catalyst systems (Cp2ZrCl2/MMT, Cp2ZrCl2/MMT‐MeGlyH+, Cp2ZrCl2/MAO/MMT, [Cp2ZrCl]+[BF4]/MMT, [Cp2ZrCl]+[BF4]−/MMT‐MeGlyH+, [Cp2ZrCl]+[BF4]−/MAO/MMT‐MeGlyH+, and [Cp2ZrCl]+[BF4]−/MAO/MMT). The polyethylenes with good bulk density were obtained from the catalyst systems, particularly (Cp2ZrCl2/MAO/MMT‐MeGlyH+). MeGlyH+and MAO seemed to play important roles for preparation of the supported zirconocenes and polymerization of ethylene. The difference in Zr loading and catalytic activity among the supported zirconocene catalysts is discussed.