Ligands for catalysts

Patent metadata

Field	Value
Publication number	US-9718900-B2
Application number	US-201414775782-A
Country	US
Kind code	B2
Filing date	Feb 21, 2014
Priority date	Mar 15, 2013
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

Catalyst systems and methods for making and using the same. A catalyst system can include a non-metallocene catalyst having the structure: wherein M is a group 4 element, each of R 13 -R 20 are independently a hydrogen or a methyl group, wherein at least one of R 13 -R 20 is a methyl group, Ar is an aryl group or a substituted aryl group, Ar′ is an aryl group or a substituted aryl group, and each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

First claim

What is claimed is:

1. A polymerization catalyst system, comprising a non-metallocene catalyst having the structure:

wherein M is a group 4 element, each of R 13 -R 20 are independently a hydrogen or a methyl group, wherein at least one of R 13 -R 2 is a methyl group, Ar is an aryl group or a substituted aryl group, Ar' is an aryl group or a substituted aryl group, and each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

2. The polymerization catalyst system of claim 1 , wherein the catalyst comprises a compound with the formula:

wherein each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

3. The polymerization catalyst system of claim 1 , further comprising bis(n-butylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

4. The polymerization catalyst system of claim 1 , further comprising (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

5. The polymerization catalyst system of claim 1 , comprising [(pentamethylbenzylN(CH 2 CH 2 )(pentamethylbenzylNCH 2 CH(CH 3 ))NH]Zr(X) 2 , wherein each X is, independently, a hydride group, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

6. The polymerization catalyst system of claim 1 , further comprising a catalyst of the formula:
Cp A Cp B MX n or Cp A (A)Cp B MX n,

wherein M is a Group 4, 5, or 6 atom; Cp A and Cp B are each bound to M and are independently selected from the group consisting of cyclopentadienyl ligands, substituted cyclopentadienyl ligands, ligands isolobal to cyclopentadienyl and substituted ligands isolobal to cyclopentadienyl; (A) is a divalent bridging group bound to both Cp A and Cp B selected from the group consisting of divalent C 1 to C 20 hydrocarbyls and C 1 to C 20 heteroatom containing hydrocarbonyls, wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; X is a leaving group selected from the group consisting of chloride ions, bromide ions, C 1 to C 10 alkyls, and C 2 to C 12 alkenyls, carboxylates, acetylacetonates, and alkoxides; and n is an integer from 1 to 3.

7. The polymerization catalyst system of claim 1 , further comprising a catalyst of the formula:

wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal; each X is independently an anionic leaving group; y is 0 or 1; n is the oxidation state of M; m is the formal charge of the ligand represented by YZL or YZL'; L is a Group 15 or 16 element; L' is a group 15 or 16 element or Group 14 containing group; Y is a Group 15 element; Z is a Group 15 element; R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; R 1 and R 2 may be interconnected to each other; R 3 is absent, a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group; R 4 and R 5 are independently an alky group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a multiple ring system; R 4 and R 5 may be interconnected to each other; R 6 and R 7 are independently absent, hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group; and R* is absent, hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

8. The polymerization catalyst system of claim 6 , wherein two or more catalysts are co-supported on a single support.

9. The polymerization catalyst of claim 6 , wherein the non metallocene catalyst and the metallocene catalyst are co-supported on a single support, and at least a portion of the metallocene catalyst is added as a trim feed to the support.

10. The polymerization catalyst system of claim 1 , comprising a slurry mixture.

11. A method for generating an ethylene polymer, comprising polymerizing at least ethylene in the presence of a catalyst system comprising:

wherein M is a group 4 element, each of R 13 -R 20 are independently a hydrogen or a methyl group, wherein at least one of R 13 -R 20 is a methyl group, Ar is an aryl group or a substituted aryl group, Ar′ is an aryl group or a substituted aryl group, and each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

12. The method of claim 11 , wherein the catalyst system comprises a compound with the formula:

wherein each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

13. The method of claim 11 , wherein the catalyst system further comprises bis(n-butylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

14. The method of claim 11 , wherein the catalyst system further comprises (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, a hydride group an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

15. The method of claim 11 , wherein the catalyst system comprises [(pentamethylbenzylN(CH 2 CH 2 )(pentamethylbenzylNCH 2 CH(CH 3 ))NH]Zr(X) 2 , wherein each X is, independently, a hydride group, a benzyl group, a methyl group, a chloro group, a fluoro group, or a hydrocarbyl group.

16. The method of claim 11 , wherein the catalyst system further comprises a catalyst of the formula:
Cp A Cp B MX n or Cp A (A)Cp B MX n ,

wherein M is a Group 4, 5, or 6 atom; Cp A and Cp B are each bound to M and are independently selected from the group consisting of cyclopentadienyl ligands, substituted cyclopentadienyl ligands, ligands isolobal to cyclopentadienyl and substituted ligands isolobal to cyclopentadienyl; (A) is a divalent bridging group bound to both Cp A and Cp B selected from the group consisting of divalent C 1 to C 20 hydrocarbyls and C 1 to C 20 heteroatom containing hydrocarbonyls, wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; X is a leaving group selected from the group consisting of chloride ions, bromide ions, C 1 to C 10 alkyls, and C 2 to C 12 alkenyls, carboxylates, acetylacetonates, and alkoxides; and n is an integer from 1 to 3.

17. The method of claim 11 , wherein the catalyst system further comprises a catalyst of the formula:

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Assignees

• Univation Tech Llc

Inventors

• Giesbrecht Garth R

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/65922

  containing at least two cyclopentadienyl rings, fused or not · CPC title

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title