State of Titanium in Supported Titanium-Magnesium Catalysts for Propylene Polymerization
Kinetics and Catalysis
, E-ISSN: 1608-3210
Boreskov Institute of Catalysis SB RAS
The oxidation state of titanium and the coordination state of Ti3+ ions in TiCl4/D1/MgCl2 (D1 is a phthalate) supported titanium-magnesium catalysts (TMCs) after the interaction with an AlEt3/D2 cocatalyst (D2 is propyltrimethoxysilane or dicyclopentyldimethoxysilane) were studied by chemical analysis and EPR spectroscopy. Different oxidation state distributions of titanium ions were observed in the activated catalyst and mother liquor: Ti3+ and Ti2+ ions were predominant in the activated catalyst and mother liquor, respectively. The effects of interaction conditions (reaction temperature and time and Al/Ti and D2/Ti molar ratios) of TMCs with the cocatalyst on the state of titanium in activated samples were studied. The interaction of TMCs with the cocatalyst decreased the titanium content and caused the appearance of aluminum in the activated sample, which was most clearly pronounced at a temperature of 25°C and occurred within the first 10 min of treatment. An increase in the temperature to 70°C and an increase in the interaction time to 60 min only slightly affected the concentrations of titanium and aluminum. The presence of D2 as a cocatalyst constituent facilitated the removal of titanium compounds and restricted the adsorption of aluminum compounds on the catalyst surface. The main fraction of titanium consisted of Ti3+ ions (62–89%), and the rest was Ti4+ ions (22–35%) under mild interaction conditions (25°C; Si/Ti = 25) or Ti4+ (0–21%) and Ti2+ (9–21%) ions under more severe conditions (50 or 70°C; Si/Ti from 0 to 5). According to EPR-spectroscopic data, at D2/Ti from 1 to 5, Ti3+ ions mainly occurred as associates, whereas they occurred as isolated ions at D2/Ti = 25. The initial and activated catalysts were similar in activity in the reaction of propylene polymerization, and titanium compounds, which were removed from the catalyst upon interaction with AlEt3/D2, were inactive in this process.