Polymer Bulletin, Vol.72, No.10, 2471-2488, 2015
A systematic study of Nickel (II) alpha-diimine complex performance on ethylene polymerization: influence of cocatalyst nature
Ethylene polymerization was carried out with 1,4-bis(2,6-diisopropylphenyl) acenaphthene diimine-dibromo nickel (II) complex (1) combined with methyl aluminoxane (MAO) and ethylaluminium sesquichloride (EASC). The effect of three factors on three levels [temperature (10, 30, 50 A degrees C), ethylene pressure (3, 5, 7 bar) and cocatalyst to catalyst ratio (CC) (1000, 2000, 3000)] on the polymerization process was investigated individually for both cocatalysts using regression models of responses [catalyst activity, weight average molecular weight (M (w)) and crystallinity of polymer] and visualized via the response surface method (RSM). For both cocatalysts, activity responses show a second-order variation with temperature, while their pressure dependence is different. The maximum activity of catalyst 1 in the presence of EASC {3907.78 kg [(mol Ni)(-1) bar(-1) h(-1)} is higher than maximum activity in the presence of MAO {1091.89 kg [(mol Ni)(-1) bar(-1) h(-1)}. Polymerization conditions for reaching the maximum M (w) are the same for both cocatalysts (10 A degrees C, 7 bar, 3000); it is about 1,330,000 g mol(-1) for MAO and 1,512,297 g mol(-1) for EASC. Crystallinity responses reveal that EASC concentration has more significant influence on branching content of final polymer especially at lower polymerization temperature. For example at 10 A degrees C and 3 bar, the increase of EASC concentration from 1000 to 3000 leads to the increase of crystallinity from 32 to 45 %. The obtained models provided a promising tool for designing the polymer properties by replacement of MAO with other cocatalysts.
Keywords:Nickel (II) alpha-diimine complex;Polyethylene (PE);Ethyl aluminium sesquichloride;Response surface method;Regression model;Surface and contour plot