Functionalized polystyrene as a versatile support for olefin polymerization catalysts

Heterogeneous polyolefin catalysts based on metallocenium salts of weakly coordinating anions can be prepared via a series of simple reactions from lightly crosslinked chloromethylated polystyrene beads. Catalytic sites are distributed homogeneously throughout the polystyrene particles. The nonporous nature of these catalysts affords a high degree of control over the olefin uptake rate, avoiding problems of premature catalyst fragmentation that often plague high-surface-area heterogeneous catalysts based on highly reactive species. The choice of amine as the means of binding or templating allows catalysts based on a wide variety of metallocenes to be readily prepared by the same synthetic approach. The dative interactions between the metallocene cation and the amine functionality of the support material are sufficient to prevent extraction under polymerization conditions to yield excellent particle morphology of the polyolefin product, but they are not so strong as to affect the nature of the polyolefin produced. The polymer-supported catalysts have been used effectively for the polymerization of ethylene and polypropylene.