IP Library › Granted Patent US 10,882,932

Granted Patent B2

US 10,882,932 · App. 15/706,088 · Granted Jan 5, 2021

Sterically hindered metallocenes, synthesis and use

Inventors: Donna J. Crowther (Blairsville, GA); Laughlin G. McCullough (League City, TX); Jacqueline A. Lovell (Crosby, TX)

Assignee: ExxonMobil Chemical Patents Inc.

C08F210/02 C08F4/02 C08F210/14 C08F4/65912 C08F4/65916

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Quick Facts

Patent No.: US 10,882,932
App. No.: 15/706,088
Granted: Jan 5, 2021
Kind: B2

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Abstract

In at least one embodiment, a catalyst compound is represented by Formula (I): where M is a group 4 metal. Each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, or a linear or branched C 1 -C 50 substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl. At least one of R 1 and R 3 is not hydrogen. Each X is independently a halide or C 1 -C 50 substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or a combination thereof, or two Xs are joined together to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene.

Claims (72)

1. A catalyst system comprising an activator, a fluorided silica support, and a catalyst compound represented by Formula (I):

wherein M is Zr,

each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, or a linear or branched C 1 -C 50 substituted or unsubstituted hydrocarbyl, a halocarbyl or a silylcarbyl, wherein at least one of R 1 and R 3 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl, and

2. The catalyst system of claim 1 , wherein R 1 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl.

3. The catalyst system of claim 1 , wherein R 3 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl.

4. The catalyst system of claim 1 , wherein each of R 1 and R 3 is independently a linear or branched C 1 -C 5 unsubstituted hydrocarbyl.

5. The catalyst system of claim 1 , wherein each X is independently a halide or a C 1 -C 10 substituted or unsubstituted hydrocarbyl.

6. The catalyst system of claim 1 , wherein R 10 is hydrogen or a C 1 -C 10 substituted or unsubstituted hydrocarbyl, and wherein each of R 11 , R 12 , R 13 , and R 14 is independently a C 1 -C 10 substituted or unsubstituted hydrocarbyl.

7. A catalyst system comprising an activator, a fluorided silica support, and a catalyst compound represented by Formula (I):

wherein M is Zr,

each X is independently a halide or a C 1 -C 50 substituted or unsubstituted hydrocarbyl, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, a diene, an amine, a phosphine, an ether, or a combination thereof wherein two Xs are optionally joined together to form a metallocycle ring, or two Xs are optionally joined to form a chelating ligand, a diene ligand, or an alkylidene, where the support material has been slurried in a non-polar solvent and the resulting slurry was first contacted with the activator for a period of time between about 0.5 hours and about 24 hours, isolated, and then contacted with a solution of at least one catalyst compound represented by Formula (I).

8. The catalyst system of claim 1 , wherein R 1 is linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl; R 3 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl; each X is independently a halide or a C 1 -C 10 substituted or unsubstituted hydrocarbyl; and R 10 is hydrogen or a C 1 -C 10 substituted or unsubstituted hydrocarbyl, and wherein each of R 11 , R 12 , R 13 , and R 14 is independently a C 1 -C 10 substituted or unsubstituted hydrocarbyl.

9. The catalyst system of claim 1 , wherein the support material is slurried in a non-polar solvent and the resulting slurry is contacted with the activator for a period of time from about 0.5 hours to about 24 hours, then is contacted with a solution of the catalyst compound.

10. The catalyst system of claim 1 , wherein the activator comprises an alumoxane.

11. The catalyst system of claim 7 , wherein the slurry is contacted with the activator for a period of time from about 2 hours to about 16 hours.

12. The catalyst system of claim 7 , wherein the slurry is contacted with the activator for a period of time from about 2 hours to about 8 hours.

13. The catalyst system of claim 7 , wherein the non-polar solvent is selected from the group consisting of: alkanes and cycloalkanes.

14. The catalyst system of claim 7 , wherein the non-polar solvent is selected from the group consisting of: isopentane, hexane, n-heptane, octane, nonane, decane, and cyclohexane.

15. The catalyst system of claim 7 , wherein the non-polar solvent is selected from the group consisting of: alkanes and cycloalkanes.

16. A catalyst system comprising an activator, a fluorided silica support, and a catalyst compound represented by Formula (I):

wherein M is Zr,

each X is independently a halide or a C 1 -C 50 substituted or unsubstituted hydrocarbyl, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, a diene, or a combination thereof, wherein two Xs are optionally joined together to form a metallocycle ring, or two Xs may be joined to form a chelating ligand, a diene ligand, or an alkylidene.

17. The catalyst system of claim 16 , wherein R 1 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl.

18. The catalyst system of claim 16 , wherein R 3 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl.

19. The catalyst system of claim 16 , wherein each of R 1 and R 3 is independently a linear or branched C 1 -C 5 unsubstituted hydrocarbyl.

20. The catalyst system of claim 16 , wherein each X is independently a halide or a C 1 -C 10 substituted or unsubstituted hydrocarbyl.

21. The catalyst system of claim 16 , wherein R 10 is hydrogen or a C 1 -C 10 substituted or unsubstituted hydrocarbyl, and wherein each of R 11 , R 12 , R 13 , and R 14 is independently a C 1 -C 10 substituted or unsubstituted hydrocarbyl.

22. The catalyst system of claim 16 , wherein R 1 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl; R 3 is a linear or branched C 1 -C 10 substituted or unsubstituted hydrocarbyl; each X is independently a halide or a C 1 -C 10 substituted or unsubstituted hydrocarbyl; and R 10 is hydrogen or a C 1 -C 10 substituted or unsubstituted hydrocarbyl, and wherein each of R 11 , R 12 , R 13 , and R 14 is independently a C 1 -C 10 substituted or unsubstituted hydrocarbyl.

23. The catalyst system of claim 16 , wherein the support material is slurried in a non-polar solvent and the resulting slurry is contacted with the activator for a period of time from about 0.5 hours to about 24 hours, then is contacted with a solution of the catalyst compound.

24. The catalyst system of claim 16 , wherein the activator comprises an alumoxane.

25. The catalyst system of claim 23 , wherein the slurry is contacted with the activator for a period of time from about 2 hours to about 16 hours.

26. The catalyst system of claim 23 , wherein the slurry is contacted with the activator for a period of time from about 2 hours to about 8 hours.

27. The catalyst system of claim 23 , wherein the non-polar solvent is selected from the group consisting of: isopentane, hexane, n-heptane, octane, nonane, decane, cyclohexane, benzene, toluene, and ethylbenzene.

28. The catalyst system of claim 23 , wherein the non-polar solvent is selected from the group consisting of: isopentane, hexane, n-heptane, octane, nonane, decane, and cyclohexane.

29. The catalyst system of claim 23 , wherein the non-polar solvents are selected from the group consisting of: alkanes and cycloalkanes.

30. The catalyst of claim 7 wherein the support has a surface area of 300 to 700 m 2 /g and a pore volume of 1.65 to 3.0 cc/g.

31. The catalyst system of claim 1 , wherein the catalyst compound represented by Formula (I) comprises one or more of:

(1,3-Me 2 -benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (1-Me-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (1-Me-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ;

(1,3-Me 2 -benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (1-Me-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (1-Me-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ;

(1,3-Et 2 -benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (1-Et-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (1-Et-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ;

(1,3-Et 2 -benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (1-Et-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (1-Et-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ;

(1,3-n-Pr 2 -benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (1-n-Pr-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (1-n-Pr-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ;

(1,3-n-Pr 2 -benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (1-n-Pr-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (1-n-Pr-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ;

(1,3-Me 2 -benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ; (3-Me-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (3-Me-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ;

(1,3-Me 2 -benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ; (3-Me-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (3-Me-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ;

(1,3-Et 2 -benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ; (3-Et-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (3-Et-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ;

(1,3-Et 2 -benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ; (3-Et-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; (3-Et-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ;

(1,3-n-Pr 2 -benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ; (3-n-Pr-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrCl 2 ; (3-n-Pr-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrCl 2 ;

(1,3-n-Pr 2 -benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 ; (3-n-Pr-benz[e]indenyl)(Me 5 cyclopentadienyl)ZrMe 2 ; and (3-n-Pr-benz[e]indenyl)(Me 4 cyclopentadienyl)ZrMe 2 .

32. The catalyst system of claim 7 , wherein the catalyst compound represented by Formula (I) comprises one or more of: