Olefin polymerization by cyclopentadienyltris(dimethylamido)titanium(IV) complexes

Several titanium(IV) complexes of the type Cp'Ti(NMe2)(3) [Cp' = cyclopenta dienyl (1), (dimethylaminoethyl)cyclopentadienyl (2), indenyl (3), and pent amethylcyclopentadienyl (4)] were prepared, and their catalytic properties in the polymerization of alpha -olefins were examined. Complexes 1 and 2 ca talyzed the polymerization of ethylene in the presence of methylaluminoxane with a much higher activity than 3 or 4. Complexes 3 and 4 polymerized eth ylene with an activity similar to that of CpTiCl3 (6). The preactivation of 2, 3, or 4 with trimethylaluminum (TMA) resulted in an increase in ethylen e polymerization activities. Also, 1 and 2 were successfully used as ethyle ne/1-hexene copolymerization catalysts, producing polymers with various amo unts of l-hexene incorporation, depending on the amount of l-hexene in the feed mixture. Complex 1 likewise effectively polymerized styrene with a hig her activity and higher syndiospecificity than the other three catalysts. C omplexes 3 and 4 polymerized styrene with low syndiospecificity, whereas 2 produced only atactic polystyrene. The preactivation of 3 or 4 with TMA res ulted in an increase in styrene polymerization activities and increased the syndiotacticity percentage of the polymers produced. (C) 2000 John Wiley & Sons, Inc.