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New organic supports for metallocene catalysts applied in olefin polymerizations
Author(s) -
Klapper Markus,
Jang YongJun,
Bieber Kirsten,
Nemnich Tanja,
Nenov Nikolay,
Müllen Klaus
Publication year - 2004
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200450914
Subject(s) - polyolefin , polymerization , materials science , metallocene , monomer , polymer chemistry , surface modification , miniemulsion , copolymer , styrene , catalysis , olefin fiber , organic chemistry , chemistry , polymer , nanotechnology , layer (electronics)
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. [Me 2 Si(2MeBenzInd) 2 ZrCl 2 /MAO] on PPO containing latices or Cp 2 ZrMe 2 /([Ph 3 C][B(C 6 F 5 ) 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.