Trägerkatalysatoren aus C12‐allylnickel(II)‐komplexen [Ni(C12H19)]X (X = SbF6, O3SCF3) und amorphem aluminiumfluorid in toluol als modell‐katalysatoren für das technische katalysatorsystem Ni(octanoat)2/BF3·OEt2/AlEt3 zur 1,4‐cis‐polymerisation des butadiens

Abstract

AbstractThe η3, η2, η2‐dodeca‐2(E), 6(E), 10(Z)‐trien‐1‐yl‐nickel(II) complexes [Ni(C12H19)]X (X = SbF6, O3SCF3) were treated in toluene with amorphous aluminium trifluoride (which was prepared from AlEt3 and BF3 · OEt2) in a mole ratio 1 : 10 to 20, forming a highly active catalyst for the 1,4‐cis polymerization of butadiene. This catalyst is comparable in its activity and selectivity, and in the molar mass distribution of the polybutadiene, with the technical nickel catalyst Ni(O2CR)2/BF3ċOEt2/AlE3 developed by Bridgestone Tire Company thirty years ago. The existence of the C12‐allynickel(II) cation [Ni(C12H19)]+ on the AlF3 support could be proved by FAB mass spectroscopic measurements. In agreement with our reaction model for the allyl nickel complex catalyzed butadiene polymerization, it is concluded that the technical nickel catalyst in its effective structure can be described as a polybutadienylnickel(II) complex co‐ordinated to a polymeric fluoroaluminate anion via a fluoride bridge.