Supported catalyst for olefin polymerization
View Patent ↗Disclosed are catalyst systems and methods of making the catalyst systems for the polymerization of an olefin containing a solid titanium catalyst component containing an inorganic titanium compound, a magnesium alcohol adduct made from an inorganic magnesium compound and an alcohol, and a porous support having at least one of a certain specific surface area, a certain pore volume, and a certain median particle size. The catalyst system may further contain an organoaluminum compound and optionally an organosilicon compound. Also disclosed are methods of making polyolefins.
1. A solid titanium catalyst component for the polymerization of olefins, comprising:
an inorganic titanium compound;
a magnesium alcohol adduct made by contacting an inorganic magnesium compound, an alcohol, and an organic medium, wherein the alcohol and the inorganic magnesium compound are contacted at a molar ratio of the alcohol to the inorganic magnesium compound from about 0.1:1 to about 1:0.1, and wherein the organic medium and the inorganic magnesium compound are contacted at a molar ratio of the organic medium to the inorganic magnesium compound from about 1:1 to about 50:1; and
a porous support having at least one of a specific surface area of about 100 m 2 /g or more and about 2,000 m 2 /g or less, a pore volume of about 0.2 cc/g or more and about 5 cc/g or less, and a median particle size (by volume) of about 1 micron or more and about 200 microns or less,
the solid titanium catalyst component having a diameter from about 20 microns to about 150 microns (on a 50% by volume basis).
2. The solid titanium catalyst component of claim 1 , wherein the porous support has at least two of a specific surface area of about 200 m 2 /g or more and about 1,500 m 2 /g or less, a pore volume of about 0.3 cc/g or more and about 4 cc/g or less, and a median particle size (by volume) of about 5 microns or more and about 150 microns or less.
3. The solid titanium catalyst component of claim 1 , wherein the porous support has a specific surface area of about 300 m 2 /g or more and about 1,000 m 2 /g or less, a pore volume of about 0.5 cc/g or more and about 3 cc/g or less, and a median particle size (by volume) of about 10 microns or more and about 100 microns or less.
4. The solid titanium catalyst component of claim 1 , wherein the porous support comprises at least one selected from the group consisting of silica, alumina, alumina-silicates, ceria, zeolites, clay, zirconia, titania, zinc oxide.
5. The solid titanium catalyst component of claim 1 , wherein the inorganic magnesium compound is at least one selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, and the inorganic titanium compound comprises at least one selected from the group consisting of titanium chloride, titanium bromide, titanium iodide, and titanium fluoride.
6. The solid titanium catalyst component of claim 1 , wherein the alcohol comprises an alkyl alcohol containing from 1 to about 12 carbon atoms.
7. The solid titanium catalyst component of claim 1 further comprising an internal electron donor.
8. The solid titanium catalyst component of claim 1 , wherein the magnesium alcohol adduct is not dealcoholed.
9. The solid titanium catalyst component of claim 1 , wherein the porous support comprises at least one selected from the group consisting of silica, alumina, alumina-silicates, ceria, zeolites, clay, zirconia, titania, zinc oxide.
10. The solid titanium catalyst component of claim 1 , wherein the alcohol comprises an alkyl alcohol containing from 1 to about 12 carbon atoms.
11. The solid titanium catalyst component of claim 1 , wherein the magnesium-alcohol adduct is made by contacting the alcohol and the inorganic magnesium at a molar ratio of the alcohol to the inorganic magnesium compound of about 0.1:1 to about 1:0.1.
12. A solid titanium catalyst component for the polymerization of olefins, consisting essentially of:
an inorganic titanium compound; a magnesium alcohol adduct made from an inorganic magnesium compound and an alcohol; and
a porous support having at least one of a specific surface area of about 100 m 2 /g or more and about 2,000 m 2 /g or less, a pore volume of about 0.2 cc/g or more and about 5 cc/g or less, and a median particle size (by volume) of about 1 micron or more and about 200 microns or less,
the solid titanium catalyst component having a diameter from about 20 microns to about 150 microns (on a 50% by volume basis).
13. A method of making a solid titanium catalyst component for the polymerization of olefins, comprising:
combining an inorganic magnesium compound, an alcohol, and an organic medium to form a magnesium alcohol adduct, wherein the alcohol and the inorganic magnesium compound are contacted at a molar ratio of the alcohol to the inorganic magnesium compound from about 0.1:1 to about 1:0.1, and wherein the organic medium and the inorganic magnesium compound are contacted at a molar ratio of the organic medium to the inorganic magnesium compound from about 1:1 to about 50:1;
impregnating the adduct onto a porous support having at least one of a specific surface area of about 100 m 2 /g or more and about 2,000 m 2 /g or less, a pore volume of about 0.2 cc/g or more and about 5 cc/g or less, and a median particle size (by volume) of about 1 micron or more and about 200 microns or less; and
contacting the adduct impregnated porous support with an inorganic titanium compound.
14. The method of claim 13 , wherein the porous support has a specific surface area of about 300 m 2 /g or more and about 1,000 m 2 /g or less, a pore volume of about 0.5 cc/g or more and about 3 cc/g or less, and a median particle size (by volume) of about 10 microns or more and about 100 microns or less.
15. The method of claim 13 , wherein the porous support comprises at least one selected from the group consisting of silica, alumina, alumina-silicates, ceria, zeolites, clay, zirconia, titania, and zinc oxide.
16. The method of claim 13 , wherein the inorganic magnesium compound is at least one selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, and the inorganic titanium compound comprises at least one selected from the group consisting of titanium chloride, titanium bromide, titanium iodide, and titanium fluoride.
17. The method of claim 13 , wherein the magnesium compound and the alcohol are heated to a temperature from about 40° C. to about 200° C.
18. The method of claim 13 , wherein the inorganic magnesium compound and the alcohol are heated for a time from about 5 minutes to about 15 hours.
19. The method of claim 13 , wherein the magnesium alcohol adduct is made by contacting the alcohol and the inorganic magnesium compound at a molar ratio of the alcohol to the inorganic magnesium compound from about 0.25:1 to about 1:0.25.
20. The method of claim 13 , wherein the organic medium is one or more selected from the group consisting of butane, pentane, hexane, heptane, octanes, decane, kerosene, cyclopentane, cyclohexane, cyclooxtane, benzene, tolune, xylene, ethylbenzene, and napthalenes.