Comonomer enhancement effect of 1‐hexene in ethylene copolymerization catalyzed over MgCl2/THF/TiCl4 catalysts

Abstract Homo‐ and copolymerization of ethylene were performed by using a catalyst system composed of TiCl 4 /THF/MgCl 2 complex activated with AlEt 3 at 70°C and 3 atm. To investigate the effect of the compositional difference of the catalyst on the rates of homo‐ and copolymerization and on the reactivity in ethylene–hexene copolymerization, a series of six catalysts with different compositions (Mg/Ti = 0.4–16.5) were prepared by coprecipitation. The catalytic activity in ethylene polymerization increased sharply with the Mg/Ti ratio from 21 (Mg/Ti = 0.4) to 1477 kg PE/g‐Ti h (Mg/Ti = 16.5). The activity in copolymerization with 1‐hexene also increased with Mg/Ti ratio. The values of r 1 were 120, regardless of Mg/Ti ratios within the experimental error range. Enhancement of the polymerization rate by the addition of 1‐hexene in the reaction medium was observed only for the catalysts of low Mg/Ti ratio. This unusual effect of 1‐hexene on the polymerization rate was explained by chemical and physical processes that occurred during polymerization. © 1993 John Wiley & Sons, Inc.