Producing polyolefin products

Patent metadata

Field	Value
Publication number	US-9809667-B2
Application number	US-201515116696-A
Country	US
Kind code	B2
Filing date	Feb 10, 2015
Priority date	Feb 11, 2014
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

Catalyst systems and methods for making and using the same. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, includes contacting ethylene and a comonomer with a catalyst system. The catalyst system includes a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system. The first catalyst compound includes a compound with the general formula (C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2 . The second catalyst compound includes at least one of the following general formulas: In both catalyst systems, the R groups can be independently selected from any number of substituents, including, for example, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, among others.

First claim

What is claimed is:

1. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, comprising contacting ethylene and a comonomer with a catalyst system, wherein the catalyst system comprises a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula:
(C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2
wherein each R 1 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are >3; a+b =c+d =5; at least one R 1 and at least one R 2 is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R 1 and R 2 groups are optionally coupled to form a ring; and each X is independently a leaving group selected from a labile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or a divalent radical that links to an R 1 or R 2 group; and the second catalyst compound comprises the following formula:

wherein each R 3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R 5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R 3 , R 4 , and R 5 are the same or different; and each X is independently a leaving group selected from a labile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or a divalent radical that links to an R 3 , R 4 , or R 5 group.

2. The method of claim 1 , wherein the value of a comonomer/ethylene incorporation ratio for the second catalyst is less than about 0.8 as large as comonomer/ethylene incorporation ratio of the first catalyst.

3. The method of claim 1 , wherein the value of the comonomer/ethylene incorporation ratio for the second catalyst is less than about 0.25 as large as a comonomer/ethylene incorporation ratio of the first catalyst.

4. The method of claim 1 , comprising continuously combining a catalyst component slurry with a catalyst component solution to form the commonly supported catalyst system.

5. The method of claim 4 , wherein the catalyst component slurry comprises the first catalyst compound and the catalyst component solution comprises the second catalyst compound.

6. The method of claim 1 , comprising adjusting a ratio of the comonomer to ethylene to control a composition distribution, a molecular weight distribution, a melt index (I 2 ), or a ratio of two melt indices, or any combinations thereof, of the polyolefin polymer.

7. A catalyst composition comprising a first catalyst compound and a second catalyst compound that are co-supported forming a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula:
(C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2
wherein each R 1 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are >3; a+b =c+d =5; at least one R 1 and at least one R 2 is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R 1 and R 2 groups are optionally coupled to form a ring; and each X is independently a leaving group selected from a labile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or a divalent radical that links to an R 1 or R 2 group; and the second catalyst compound comprises the following formula:

wherein each R 3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R 5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R 3 , R 4 , and R 5 are the same or different; wherein R 3 , R 4 , or R 5 groups are optionally joined with R 3 , R 4 , or R 5 groups on an opposing cyclopentadienyl structure to form one or more bridges if the number of atoms connecting the two cyclopentadienyl rings is >3; and each X is independently a leaving group selected from a labile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or a divalent radical that links to a R 3 , R 4 , or R 5 substituent.

8. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

9. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

10. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

wherein each R 4 is independently a methyl, ethyl, propyl, pentyl, hexyl, octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl.

11. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

12. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

13. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

14. The catalyst composition of claim 7 , wherein the first catalyst compound has the following formula:

15. The catalyst composition of claim 7 , wherein the first catalyst compound has the following formula:

16. The catalyst composition of claim 7 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 10:1 to 1:10.

17. The catalyst composition of claim 7 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 3:1 to 1:3.

18. The catalyst composition of claim 7 , comprising an organometallic agent comprising a compound of the following formula: ER 6 n R 7 V-n , wherein E is Al, B, Mg, Ca, Zn, Si, Ti, Zr, Hf; each R 6 is independently H, or a hydrocarbyl; each R 7 is independently a H, a C1 to C20 hydrocarbon group, or a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; V is the valence of E, and n is 1-V.

19. The catalyst composition of claim 7 , further comprising a catalyst compound of the following formula:

Assignees

• Univation Tech Llc

Inventors

• Lue Ching-Tai
• Rix Francis C
• Harlan C Jeff
• Mccullough Laughlin G

Classifications

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• B32B27/32

  comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)} · CPC title

• C08F2500/13

  Environmental stress cracking resistance · CPC title

• C08F2410/02

  Anti-static agent incorporated into the catalyst · CPC title

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title