Journal of Polymer Science Part A: Polymer Chemistry, Vol.55, No.5, 830-842, 2017
Thermo-stable 2-(arylimino)benzylidene-9-arylimino-5,6,7,8-tetrahydro cyclohepta[b]pyridyliron(II) precatalysts toward ethylene polymerization and highly linear polyethylenes
A series of 2-(arylimino)benzylidene-9-arylimino-5,6,7,8-tetrahydrocyclohepta[b]pyridyliron(II) chlorides was synthesized and characterized using FT-IR and elemental analysis, and the molecular structures of complexes Fe3 and Fe4 have been confirmed by the single-crystal X-ray diffraction as a pseudo-square-pyramidal or distorted trigonal-bipyramidal geometry around the iron core. On activation with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all iron precatalysts exhibited high activities toward ethylene polymerization with a marvelous thermo-stability and long lifetime. The Fe4/MAO system showed highest activity of 1.56 x 10(7) gPE.mol(-1)(Fe).h(-1) at 70 degrees C, which is one of the highest activities toward ethylene polymerization by iron precatalysts. Even up to 80 degrees C, Fe3/MAO system still persist high activity as 6.87 x 10(6) g(PE).mol(-1)(Fe).h(-1), demonstrating remarkable thermal stability for industrial polymerizations (80-100 degrees C). This was mainly attributing to the phenyl modification of the framework of the iron precatalysts. (C) 2016 Wiley Periodicals, Inc.