Polymerization catalysts
AssigneePhillips Petroleum Company
InventorsCharles M. Selman, Lawrence M. Fodor
Life of this patent
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Abstract
Polymerization catalyst preparation comprising milling magnesium metal, an organic halide and titanium tetrahalide in the presence of a triaryl phosphite and an aluminum trihalide but in the absence of a complexing diluent. The titanium catalyst component is activated with an organoaluminum activator producing a catalyst for olefin polymerization. In one embodiment, the titanium catalyst component is milled in the presence of magnesium oxide. In another embodiment, the milled titanium catalyst component is subjected to heat treatment.
Claims11
A process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule under polymerization conditions with a catalyst formed by contacting
- (a) magnesium metal,
- (b) an organic halide of the formula R'X or R"X.sub.2 where X represents a halogen, R' is selected from alkynyl, alkenyl, alkyl, aryl, cycloalkenyl or cycloalkyl radicals and combinations thereof containing from 1 to 12 carbon atoms per molecule and R" is a saturated divalent aliphatic hydrocarbyl radical having from 2 to about 10 carbon atoms and
- (c) a titanium tetrahalide and subjecting same to intensive milling in the presence of
- (d) a triaryl phosphite
- (e) an anhydrous aluminum trihalide and
- (f) magnesium oxide but in the absence of a complexing or extraneous diluent
- thereafter activating the thus produced titanium catalyst component by contacting same with
- (g) an activator comprising a trialkylaluminum compound, a dialkylaluminum chloride, and a polar organic adjuvant which is an electron donor, said adjuvant further being characterized as a 1 to 4 carbon atom alkyl ester of a substituted or unsubstituted benzoic acid.
A polymerization process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule under polymerization conditions with a catalyst formed by
- (a) combining an organic halide of the formula R'X or R"X.sub.2 where X represents a halogen, R' is selected from alkynyl, alkenyl, alkyl, aryl, cycloalkenyl or cycloalkyl radicals and combinations thereof containing from 1 to 12 carbon atoms per molecule and R" is a saturated divalent aliphatic hydrocarbyl radical having from 2 to about 10 carbon atoms with titanium tetrachloride, magnesium oxide, and magnesium metal and subjecting same to intensive milling by means of ball milling, rod milling, pebble milling, or vibratory ball milling in the absence of any extraneous diluent to produce a titanium catalyst component;
- (b) milling the entire reaction product of (a) with triphenyl phosphite and anhydrous aluminum trichloride, and
- (c) thereafter activating the thus milled titanium catalyst component product of (b) by contacting same with an activator comprising a trialkylaluminum compound, a dialkylaluminum chloride, and a polar organic adjuvant which is an electron donor, said adjuvant further being characterized as a 1 to 4 carbon atom alkyl ester of a substituted or unsubstituted benzoic acid, a mole ratio of total organoaluminum compounds to said adjuvant being within the range 2.4:1 to 3.2:1, the weight ratio of the total of organic halide, magnesium metal, and titanium tetrachloride to the total of triphenyl phosphite and aluminum trichloride being within the range from about 2 to 1 to about 200 to 1, the mole ratio of triphenyl phosphite to aluminum trichloride being about 0.03 to 1 to about 6 to 1, said magnesium metal and organic halide being introduced in a ratio within the range of 0.75:1 to 1:1 gram atoms of Mg:moles of organic halide, and wherein the atom ratio of titanium to magnesium used is within the range of 0.75:1 to 1.25:1.
Dependencies are inferred from the claim text.