Supported catalyst systems and processes for use thereof

• US 10,533,063 B2
• Filed: 03/10/2016
• Issued: 01/14/2020
• Est. Priority Date: 04/20/2015
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Ye, Xuan, Hagadorn, John R., Holtcamp, Matthew W., Day, Gregory S., Sanders, David F., Lopez-Barron, Carlos R.
• Primary Examiner(s): Cheung, William K
• Application Number:
  US15/565,603
• Publication Number:
  US 20180118860A1
• Time in Patent Office: 1,405 Days
• Field of Search: 526129
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/07 Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 2500/05 Bimodal or multimodal molecular weight distribution
• CPC Class Codes: C08F 2500/11 Melt tension or melt strength
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/13 Environmental stress cracking resistance
• CPC Class Codes: C08F 2500/18 Bulk density
• CPC Class Codes: C08F 4/025 Metal oxides
• CPC Class Codes: C08F 4/60148 NN(R)N
• CPC Class Codes: C08F 4/64148 NN(R)N
• CPC Class Codes: C08F 4/659 Component covered by group C08F4/64 containing a transition metal-carbon bond C08F4/64003 - C08F4/64196 take precedence
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 two cyclopentadienyl rings being mutually non-bridged

Abstract

This invention relates to a supported catalyst system and process for use thereof. In particular, the catalyst system includes a pyridyldiamido transition metal complex, a metallocene compound, a support material and, optionally, an activator. The catalyst system may be used for preparing multi-modal polyolefins.

Claims

1. A supported catalyst system comprising:

(i) at least one first catalyst component comprising a pyridyldiamido transition metal complex;

(ii) at least one second catalyst component comprising a metallocene compound; and

(iii) a fluorided support material,

wherein the pyridyldiamido transition metal complex has the general formula (I);

2. The supported catalyst system of claim 1, wherein the pyridyldiamido transition metal complex is represented by the formula (II):

3. The supported catalyst system of claim 1, wherein the pyridyldiamido transition metal complex is represented by the formula (III):

4. The supported catalyst system of claim 1, wherein the metallocene compound is represented by the formula Cp^ACp^BM′

X′

_n, wherein Cp^A and Cp^B may each be independently selected from the group consisting of cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, either or both Cp^A and Cp^B may contain heteroatoms, and either or both Cp^A and Cp^B may be substituted;

wherein M′

is Ti, Zr, or Hf;

wherein X′

may be any leaving group;

wherein n is 0, 1, 2, 3, or 4.

5. The supported catalyst system of claim 1, wherein the metallocene compound is selected from the group consisting of:

bis(cyclopentadienyl)zirconium dichloride,

bis(n-butylcyclopentadienyl)zirconium dichloride,

bis(n-butylcyclopentadienyl)zirconium dimethyl,

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

bis(pentamethylcyclopentadienyl)hafnium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl,

bis(tetrahydro-1-indenyl)zirconium dichloride,

bis(tetrahydro-1-indenyl)zirconium dimethyl,

(n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dichloride, and

(n-propylcyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dimethyl.

6. The supported catalyst system of claim 1, wherein the fluorided support material has a surface area in the range of from 10 to 700 m²/g and an average particle diameter in the range of from 10 to 500 μ

m.

7. The supported catalyst system of claim 1, wherein the fluorided support material is selected from the group consisting of silica, alumina, silica-alumina, and combinations thereof.

8. The supported catalyst system of claim 1, wherein the supported catalyst system further comprises an activator.

9. The supported catalyst system of claim 1, wherein the fluorided support material has a fluorine concentration in the range of 0.6 to 3.5 wt %, based upon the weight of the fluorided support material.

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

11. A process for polymerization of olefin monomers comprising contacting one or more monomers with a supported catalyst system, wherein the supported catalyst system comprises:

(i) at least one first catalyst component comprising a pyridyldiamido transition metal complex;

(ii) at least one second catalyst component comprising a metallocene compound; and

(iii) a fluorided support material,

wherein the pyridyldiamido transition metal complex has the general formula (I);

12. The process of claim 11, wherein the pyridyldiamido transition metal complex is represented by the formula (II):

13. The process of claim 11, wherein the pyridyldiamido transition metal complex is represented by the formula (III):

14. The process of claim 11, wherein the metallocene compound is represented by the formula Cp^ACp^BM′

X′

_n, wherein Cp^A and Cp^B may each be independently selected from the group consisting of cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, either or both Cp^A and Cp^B may contain heteroatoms, and either or both Cp^A and Cp^B may be substituted;

wherein M′

is Ti, Zr, or Hf;

wherein X′

may be any leaving group;

wherein n is 0, 1, 2, 3, or 4.

15. The process of claim 11, wherein the metallocene compound is selected from the group consisting of:

bis(cyclopentadienyl)zirconium dichloride,

bis(n-butylcyclopentadienyl)zirconium dichloride,

bis(n-butylcyclopentadienyl)zirconium dimethyl,

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

bis(pentamethylcyclopentadienyl)hafnium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl,

bis(tetrahydro-1-indenyl)zirconium dichloride,

bis(tetrahydro-1-indenyl)zirconium dimethyl,

(n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dichloride, and

(n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dimethyl.

16. The process of claim 11, wherein the fluorided support material has a surface area in the range of from 10 to 700 m²/g and an average particle diameter in the range of from 10 to 500 μ

m.

17. The process of claim 11, wherein the fluorided support material is selected from the group consisting of silica, alumina, silica-alumina, and combinations thereof.

18. The process of claim 11, wherein the supported catalyst system further comprises an activator.

19. The process of claim 11, wherein the fluorided support material has a fluorine concentration in the range of 0.6 to 3.5 wt %, based upon the weight of the fluorided support material.

20. The process of claim 11, wherein the first catalyst component and the second catalyst component show different hydrogen responses.

21. The process of claim 11, wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-hexene, 1-octene and combinations thereof.

22. The process of claim 11, wherein the polymerization is carried out in slurry.