IP Library Granted Patent US 7,326,757
Granted Patent B2
US 7,326,757 · App. 11/185,126 · Granted Feb 5, 2008

Supported catalyst for olefin polymerization

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Quick Facts
Patent No.
US 7,326,757
App. No.
11/185,126
Granted
Feb 5, 2008
Kind
B2
Abstract

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.

Claims (28)

1. A catalyst system for the polymerization of an olefin, comprising:

a solid titanium catalyst component consisting essentially of an inorganic titanium compound, a magnesium-alcohol adduct, 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;

an organoaluminum compound having at least one aluminum-carbon bond; and

optionally an organosilicon compound.

2. The catalyst system 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 weight) of about 5 microns or more and about 150 microns or less.

3. The catalyst system of claim 1 , wherein the inorganic titanium compound comprises at least one selected from the group consisting of titanium chloride, titanium bromide, titanium iodide, and titanium fluoride.

4. The catalyst system of claim 1 , wherein the alcohol comprises at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, t-butanol, n-pentanol, iso-pentanol, hexanol, 2-ethylhexanol, decanol, cyclohexanol, and phenol.

5. The catalyst system of claim 1 , wherein the solid titanium catalyst component further comprises an internal electron donor.

6. The catalyst system of claim 1 , wherein the magnesium-alcohol adduct is made from an alcohol and an inorganic magnesium compound selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride.

7. The catalyst system of claim 1 , wherein the solid titanium catalyst component has a diameter from about 25 microns to about 100 microns (on a 50% by volume basis).

8. The catalyst system of claim 1 , wherein the magnesium alcohol adduct is not dealcoholed.

9. The catalyst system 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.

10. The catalyst system 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.

11. The catalyst system of claim 1 , wherein the alcohol comprises an alkyl alcohol containing from 1 to about 12 carbon atoms.

12. The catalyst system of claim 6 , 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.

13. The catalyst system of claim 6 , 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 0.25:1 to about 1:0.25.

14. The catalyst system of claim 6 , 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 0.5:1 to about 1:0.5.

15. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium to a temperature from about 40° C. to about 200° C.

16. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium to a temperature from about 60° C. to about 140° C.

17. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium to a temperature from about 80° C. to about 120° C.

18. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium for a time from about 5 minutes to about 15 hours.

19. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium for a period of time from about 30 minutes to about 10 hours.

20. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium for a period of time from about 1 hour to about 4 hours.

21. The catalyst system of claim 6 , wherein the magnesium-alcohol adduct is made by heating the alcohol and the inorganic magnesium and then recovering precipitation.

22. A method of making a polyolefin, comprising:

contacting an olefin with a catalyst system comprising a solid titanium catalyst component, the solid titanium catalyst component 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; a organoaluminum compound having at least one aluminum-carbon bond; and optionally an organosilicon compound to provide the polyolefin.

23. The method of claim 22 , wherein the olefin comprises at least one selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene, 1-eicosene, and vinylcyclohexane.

24. The method of claim 22 , wherein the solid titanium catalyst component further comprises an internal electron donor.

Assignments (7)
SECURITY INTEREST Recorded Feb 17, 2023
From: W.R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 062792/0510 →
TERM LOAN SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 057594/0104 →
NOTES SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 057594/0156 →
RELEASE OF SECURITY INTEREST Recorded Sep 23, 2021
From: GOLDMAN SACHS BANK USA
To: W. R. GRACE & CO.-CONN.
Reel/Frame 057594/0026 →
SECURITY INTEREST Recorded Apr 3, 2018
From: W. R. GRACE & CO.-CONN.
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 045828/0683 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 22, 2016
From: BASF CORPORATION
To: W. R. GRACE & CO. - CONN.
Reel/Frame 040255/0136 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 20, 2005
From: ZHU, ZHIDONG; CHANG, MAIN
To: ENGELHARD CORPORATION
Reel/Frame 016789/0511 →