New organic supports for metallocene catalysts applied in olefin polymerizations

Nano-sized latex particles as organic supports for metallocenes applied in olefin polymerizations are introduced. The particles are functionalized with nucleophilic surfaces such as polyethylenoxide (PEO), polypropyleneoxide (PPO) or pyridine units allowing an immobilization of the metallocene catalysts via a non-covalent immobilization process. The latices are obtained by emulsion or miniemulsion polymerization with styrene, divinylbenzene as the crosslinker, and either PEO or PPO functionalized styrene or 4-vinylpyridine for surface functionalization. The supported catalysts, e.g. Me₂Si(2MeBenzInd)₂ZrCl₂/MAO] on PPO containing latices or Cp₂ZrMe₂/(Ph₃C]B(C₆F₅)₄]) on pyridine functionalized materials were tested in ethylene polymerizations. Remarkably, high activities and excellent product morphologies were obtained. The influence of the degree of surface functionalization on activity and productivity was investigated. Furthermore, the fragmentation of the catalyst was studied by electron microscopy using bismuth-labeled latex particles or by fluorescence and confocal fluorescence microscopy using dye-labeled supports. Finally, a self-immobilizing catalyst/monomer system is presented. It is demonstrated that by using PEO-functionalized olefins, the metallocenes were immobilized on the monomers. Subjecting these mixtures to an ethylene copolymerization, again high activities and productivities as well as polyolefin beads with high bulk densities are observed, indicating that an extra supporting process for controlling the product size and shape of the polyolefins is not necessary for these monomers.