METALLOCENE BORATE-CATALYZED POLYMERIZATION OF AMINO-FUNCTIONALIZED ALPHA-OLEFINS/

Cationic metallocene/borate catalysts, generated from zirconocene dime thyl compounds, LnZrMe2, and anilinium berate, [HNMe2Ph](+)[B(C6F5)(4) ](-), were used to polymerize 5-amino-1-pentenes and one 4-amino-1-but ene with dimethyl, diethyl, diisopropyl, or diphenyl substitution patt erns on nitrogen. The monomer 5-(N,N-diisopropylamino)-1-pentene showe d the highest activity with Cp-2ZrMe2/borate and was used for all fur ther investigations. The catalytic system Cp-2ZrMe2/borate was 4 time s more active than the corresponding methylaluminoxane-based system an d 180 times more active than the heterogeneous system, TiCl3/Al(i-Bu)( 3). 1-Hexene and 5-(N,N-diisopropylamino)-1-pentene were polymerized w ith Cp-2ZrMe2 and rac-ethylenebis(tetrahydroindenyl) zirconium dimeth yl, rac-EB(THI)ZrMe2. Polymerization of both monomers with Cp-2ZrMe2 displayed similar activities. Hexene polymerizations with rac-EB(THI)Z rMe2 were 30 times more active than those with aminopentene. 5-(N,N-Di isopropylamino)-1-pentene polymerizations gave rise to isotactic poly( aminopentene) with C-2 symmetric catalysts, syndiotactic polymer with a C-s symmetric catalyst, and atactic polymer with achiral catalyst pr ecursors.