IP Library Granted Patent US 8,354,485
Granted Patent B2
US 8,354,485 · App. 12/201,985 · Granted Jan 15, 2013

Aluminoxane catalyst activators derived from dialkylaluminum cation precursor agents, processes for making same, and use thereof in catalysts and polymerization of olefins

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Quick Facts
Patent No.
US 8,354,485
App. No.
12/201,985
Granted
Jan 15, 2013
Kind
B2
Abstract

Compositions useful for activating catalysts for olefin polymerization, and methods for making same, are provided. Such compositions can be derived from at least: an organoaluminum compound, a carrier, an oxygen source, and, optionally, a Lewis base.

Claims (52)

1. A composition derived from at least:

a) an intermediate composition derived from at least an organoaluminum compound, a carrier, and an oxygen source; and

b) R 2 2 AlY, wherein each R 2 independently comprises a hydrocarbyl group having from 1 to about 20 carbons, and Y comprises a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical.

2. The composition of claim 1 , wherein the carrier comprises an inorganic oxide.

3. The composition of claim 2 wherein the inorganic oxide comprises silica, alumina, silica-alumina, magnesia, titania, zirconia, or clays.

4. The composition of claim 2 wherein the inorganic oxide comprises silica.

5. The composition of claim 1 wherein the organoaluminum compound comprises trimethyl aluminum, tri ethyl aluminum, or triisobutylaluminum.

6. The composition of claim 1 wherein the R 2 2 AlY comprises dimethylaluminum halide.

7. The composition of claim 1 wherein the R 2 2 AlY comprises dialkylaluminum fluoride.

8. The composition of claim 1 wherein the R 2 2 AlY comprises dimethylaluminum fluoride.

9. The composition of claim 1 , wherein the composition is further derived from a Lewis base.

10. A catalyst composition for olefin polymerization, wherein the catalyst composition is prepared by combining at least a composition according to claim 1 and a transition metal component.

11. A composition derived from at least:

a) an intermediate composition derived from at least a carrier and an oxygenated organoaluminum compound; and

b) R 2 2 AlY, wherein each R 2 independently comprises a hydrocarbyl group having from 1 to about 20 carbon atoms, and Y comprises a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical.

12. A composition derived from at least:

a) an intermediate composition derived from at least a carrier and an oxygenated organoaluminum compound;

b) R 2 2 AlY, wherein each R 2 independently comprises a hydrocarbyl group having from 1 to about 20 carbon atoms, and Y comprises a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical; and

c) a Lewis base.

13. A catalyst composition for olefin polymerization, wherein the catalyst composition is prepared by combining at least a composition according to claim 11 and a transition metal component.

14. A method of preparing a composition comprising:

a) combining at least an organoaluminum compound, a carrier, and an oxygen source to form an intermediate composition; and

b) combining at least a portion of the intermediate composition with R 2 2 AlY, wherein each R 2 independently comprises a hydrocarbyl group having from 1 to about 20 carbons, and Y comprises a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical.

15. A method of preparing a composition comprising combining at least:

a) an intermediate composition derived from at least a carrier and an oxygenated organoaluminum compound; and

b) R 2 2 AlY, wherein each R 2 independently comprises hydrocarbyl group having from 1 to about 20 carbon atoms, and Y comprises a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical.

16. A method of preparing a composition comprising combining at least:

a) an intermediate composition derived from at least a carrier and an oxygenated organoaluminum compound;

b) R 2 2 AlY, wherein each R 2 independently comprises hydrocarbyl group having from 1 to about 20 carbon atoms, and Y comprises a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical; and

c) Lewis base.

17. A method of polymerizing monomer comprising combining a composition according to claim 1 , a transition metal component, and monomer.

18. A composition derived from at least:

a) an intermediate composition derived from at least an organoaluminum compound and an oxygen source; and

b) R 2 2 AlY, wherein each R 2 independently comprises hydrocarbyl group having from 1 to about 20 carbons, and Y consists essentially of an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, or a diaryl boronoxy radical.

19. A composition derived from at least:

a) an intermediate composition derived from at least an organoaluminum compound and an oxygen source;

b) R 2 2 AlY, wherein each R 2 independently comprises hydrocarbyl group having from 1 to about 20 carbons, and Y consists essentially of an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, or a diaryl boronoxy radical; and

c) a Lewis base.

20. A catalyst composition for olefin polymerization, wherein the catalyst composition is prepared by combining at least a composition according to claim 18 and a transition metal component.

21. A method of polymerizing monomer comprising combining a composition according to claim 18 , a transition metal component, and monomer.

22. A composition according to claim 1 having one of the following structures:

wherein is a bulk aluminoxane (AO) structure, each R B , R P , and R 2 is independently a hydrocarbyl group having up to about 20 carbon atoms, and each Y is independently a halide radical, a pseudo halide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical, a diaryl boronoxy radical, or a halogenated diaryl boronoxy radical;

and a carrier, wherein said carrier is attached to said bulk aluminoxane structure.

23. The composition of claim 22 , wherein each R B , R P , and R 2 is methyl or iso-butyl.

24. The composition of claim 23 , wherein Y is halide radical, alkoxide radical or aryloxide radical.

25. The composition of claim 24 , wherein Y is methoxide radical, ethoxide radical, isobutoxide radical, tert-butoxide radical, phenoxide radical, 2,6-di-tert-butyl-4-methyl-phenoxide radical, pentafluorophenoxide radical or fluoride.

26. The composition of claim 22 , wherein the composition has the structure of Formula I or Formula II.

27. The composition of claim 26 , wherein each R B , R P , and R 2 is methyl or iso-butyl and Y is a methoxide radical, tert-butoxide radical, phenoxide radical or pentafluorophenoxide radical, or fluoride.

28. A composition comprising the composition of claim 22 , and a transition metal component.

29. The composition of claim 22 , wherein said carrier is silica.

30. The composition of claim 22 , wherein the mole ratio of Y to the aluminum in the bulk aluminoxane structure is about 1:30 to about 8:25.

31. The composition of claim 22 , wherein each Y is independently an alkoxide radical, an aryloxide radical, an alkyl substituted amide radical, an aryl substituted amide radical, a siloxy radical, a boronoxy radical or a diaryl boronoxy radical.

Assignments (7)
RELEASE OF SECURITY INTEREST SUPPLEMENT NO. 1, RECORDED AT REEL/FRAME 063237/0252 Recorded Feb 2, 2026
From: WILMINGTON TRUST, NATIONAL ASSOCIATION
To: W. R. GRACE & CO.-CONN.
Reel/Frame 074612/0939 →
NOTES SECURITY INTEREST Recorded Jan 29, 2026
From: W. R. GRACE & CO.-CONN.; ADVANCED REFINING TECHNOLOGIES LLC
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 074532/0229 →
SECURITY AGREEMENT (NOTES) Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 072520/0653 →
SECURITY INTEREST Recorded Apr 2, 2023
From: W. R. GRACE & CO.-CONN.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 063237/0262 →
SECURITY INTEREST Recorded Apr 2, 2023
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 063237/0252 →
SECURITY INTEREST Recorded Feb 17, 2023
From: W.R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 062792/0510 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 31, 2018
From: ALBEMARLE CORPORATION
To: W. R. GRACE & CO-CONN.
Reel/Frame 045946/0786 →