Catalyst systems and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-10280233-B2
Application number	US-201715600138-A
Country	US
Kind code	B2
Filing date	May 19, 2017
Priority date	Jun 5, 2015
Publication date	May 7, 2019
Grant date	May 7, 2019

Abstract

Olefin polymerization catalyst systems and methods for making and using the same are provided.

First claim

What is claimed is:

1. An olefin polymerization catalyst system comprising a silica support, wherein the silica support comprises agglomerates of silica gel particles having:
a. an average surface area of from about 400 to 800 m 2 /g;
b. an average pore diameter of from about 60 to 180 angstrom;
c. at least 20% of the incremental pore volume comprised of pores having a pore diameter larger than about 100 angstrom;
d. a volume percent of pores with a pore size of from 300 to 1500 angstroms from 1.0 vol % to 95 vol %;
e. a particle size of 30 to 200 micrometers; and
f. an average pore volume of from about 0.5 to 2.5 ml/g of silica;

wherein the catalyst system further comprises an aluminoxane, and the aluminoxane loading on the support is greater than about 9.5 mmol Al/g silica.

2. The catalyst system of claim 1 , wherein said silica gel particles have an average surface area of from about 550 to 650 m 2 /g.

3. The catalyst system of claim 1 , wherein said silica gel particles have an average pore diameter of from about 80 to 130 angstrom.

4. The catalyst system of claim 1 , wherein said silica gel particles have an average pore volume of from about 1.0 to 2.0 ml/g of silica.

5. The catalyst system of claim 1 , wherein said silica gel particles have an average particle size of from about 50 to 200 micrometers.

6. The catalyst system of claim 1 , wherein at least 50% of the incremental pore volume is comprised of pores having a pore diameter larger than about 100 angstrom.

7. The catalyst system of claim 1 , wherein said aluminoxane loading on the support is greater than about 12 mmol Al/g silica.

8. The catalyst system of claim 1 , further comprising a metallocene catalyst component.

9. The catalyst system of claim 1 , wherein a raw silica surface area and a supported aluminoxane surface area differ by about or less than 10%.

10. The catalyst system of claim 1 , wherein a raw silica particle size and a supported aluminoxane particle size differ by about or less than 10% on a volumetric basis.

11. The catalyst system of claim 1 , wherein the volume percent of pores with a pore size of from 300 to 1500 angstroms is from 4.0 vol % to 80 vol %.

12. The catalyst system of claim 1 , wherein the volume percent of pores with a pore size of from 300 to 1500 angstroms is from 35 vol % to 75 vol %.

13. The catalyst system of claim 1 , wherein the volume percent of pores with a pore size of from 300 to 1500 angstroms is from 40 vol % to 75 vol %.

14. A method for making an olefin polymerization catalyst system comprising contacting:
a. a silica support, wherein the silica support comprises agglomerates of silica gel particles having:
i. an average surface area of from about 400 to 800 m 2 /g;
ii. an average pore diameter of from about 60 to 180 angstrom;
iii. at least 20% of the incremental pore volume is comprised of pores having a pore diameter larger than about 100 angstrom; and
iv. a volume percent of pores with a pore size of from 300 to 1500 angstroms from 1.0 vol % to 95 vol %;
v. a particle size of 30 to 200 micrometers; and
vi. an average pore volume of from about 0.5 to 2.5 ml/g of silica;

b. an aluminoxane; and
c. an olefin catalyst component,

wherein the catalyst system has an aluminoxane loading on the support of greater than about 9.5 mmol Al/g silica.

15. The method of claim 14 , wherein said silica gel particles have an average surface area of from about 500 to 700 m 2 /g.

16. The method of claim 14 , wherein said silica gel particles have an average pore volume of from about 1.0 to 2.0 ml/g of silica.

17. The method of claim 14 , wherein said silica gel particles have an average particle size of from about 50 to 200 micrometers.

18. The method of claim 14 , wherein at least 50% of the incremental pore volume is comprised of pores having a pore diameter larger than about 100 angstrom.

19. The method of claim 14 , wherein said aluminoxane loading is greater than about 12 mmol Al/g silica.

20. The method of claim 14 , wherein said olefin catalyst component is a metallocene catalyst component.

21. The method of claim 14 , wherein a raw silica surface area and a supported aluminoxane surface area differ by about or less than 10%, and/or wherein a raw silica particle size and a supported aluminoxane particle size differ by about or less than 10% on a volumetric basis.

22. The method of claim 14 , wherein the volume percent of pores with a pore size of from 300 to 1500 angstroms is from 4.0 vol % to 80 vol %.

23. The method of claim 14 , wherein the volume percent of pores with a pore size of from 300 to 1500 angstroms is from 35 vol % to 75 vol %.

24. The method of claim 14 , wherein the volume percent of pores with a pore size of from 300 to 1500 angstroms is from 40 vol % to 75 vol %.

25. A method for polymerizing olefins using the catalyst system of claim 1 .

26. The method of claim 14 , wherein the support is calcined from about 200° C. to about 1000° C. from about 12 hours to about 72 hours.

27. The method of claim 14 , wherein the support is calcined from about 200° C. to about 850° C. from about 24 hours to about 60 hours.

28. The catalyst system of claim 1 wherein the support comprises agglomerates of primary particles having a size range of 50 nm to 50 μm.

29. The catalyst system of claim 1 , wherein the catalyst system comprises solid particles consisting essentially of aluminoxane.

30. A method for polymerizing olefins comprising contacting olefins with the catalyst system of claim 8 in a gas phase polymerization.

31. A method for polymerizing olefins using the catalyst system of claim 8 .

32. The catalyst system of claim 8 , wherein the metallocene catalyst component is represented by the formula:

where M is a group 4, 5, or 6 metal; T is a bridging group; each X is, independently, an anionic leaving group; each R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is, independently, halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituent or a —NR′ 2 , —SR′, —OR′, —OSiR′ 3 or —PR′ 2 radical, wherein R′ is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group.

33. The catalyst system of claim 32 , wherein at least one of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is a cyclopropyl substituent represented by the formula:

wherein each R′ in the cyclopropyl substituent is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halogen.

34. The catalyst system of claim 32 , wherein M is selected from titanium, zirconium, hafnium; each X is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C 1 to C 10 alkyl groups, substituted or unsubstituted C 1 to C 10 alkoxy groups, substituted or unsubstituted C 6 to C 14 aryl groups, substituted or unsubstituted C 6 to C 14 aryloxy groups, subst

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Luo Lubin
• Jain Anupriya
• Ye Xuan

Classifications

• B01J35/1061

  Operations & Transport · mapped topic

• C08F110/06 Primary

  Propene · CPC title

• B01J35/1047

  Operations & Transport · mapped topic

• B01J37/00

  Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts · CPC title

• B01J32/00

  Operations & Transport · mapped topic