Producing polyolefin products

Patent metadata

Field	Value
Publication number	US-10174143-B2
Application number	US-201715479419-A
Country	US
Kind code	B2
Filing date	Apr 5, 2017
Priority date	Mar 15, 2013
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

Catalyst systems and methods for making and using the same are described herein. A catalyst system can include at least three catalysts. The three catalysts include a metallocene catalyst, a first non-metallocene including a ligand complexed to a metal through two or more nitrogen atoms, and a second non-metallocene including a ligand complexed to a metal through one or more nitrogen atoms and an oxygen atom.

First claim

What is claimed is:

1. A polymer comprising ethylene, wherein the polymer comprises chains formed by a polymerization catalyst system comprising at least three catalysts, comprising:
a metallocene catalyst;
a first non-metallocene comprising a ligand complexed to zirconium through three nitrogen atoms; and
a second non-metallocene comprising a catalyst of the formula:

or any combinations thereof,
wherein X 1 and X 2 are each, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group, wherein the metallocene catalyst produces a first molecular weight component, the first non-metallocene produces a second molecular weight component that has a molecular weight greater than that of the first molecular weight component, and the second non-metallocene produces a third molecular weight component that has a molecular weight greater than that of the second molecular weight component and provides a high molecular weight tail having a log molecular weight greater than 6.5.

2. The polymer of claim 1 , comprising an alpha olefin comonomer having from 5 to 20 carbon atoms.

3. The polymer of claim 1 , comprising lower molecular weight (Mw) polymer chains, mid molecular weight polymer chains, and high molecular weight polymer chains, wherein:
the lower molecular polymer chains have an average log Mw of about 3.5 to about 4.5;
the higher molecular polymer chains have an average log Mw of about 5 to about 6; and
the high molecular polymer chains have an average log Mw of about 5.5 to about 6.5.

4. The polymer of claim 3 , wherein the lower molecular weight polymer chains have an average molecular weight of less than about ¼ of the average molecular weight of the higher molecular weight polymer chains.

5. The polymer of claim 1 , comprising a polymer chain formed by a polymerization catalyst system comprising bis(n-butylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

6. The polymer of claim 1 , comprising a polymer chain formed by a polymerization catalyst system comprising (n-propylcyclopentadienyl, tetramethylcyclopentadienyl) zirconium(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

7. The polymer of claim 1 , comprising a polymer chain formed by a polymerization catalyst system comprising [(pentamethylbenzylNCH 2 ) 2 NH]Zr(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

8. The polymer of claim 1 , comprising a polymer chain formed by a polymerization catalyst system comprising [(pentamethylbenzylNCH 2 ) 2 O]Zr(X) 2 , wherein each X is, independently, phenyl, methyl, chloro, fluoro, or a hydrocarbyl group.

9. The polymer of claim 1 , comprising a polymer chain formed by a polymerization catalyst system 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.

10. The polymer of claim 1 , comprising a polymer chain formed by a polymerization catalyst system 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.

11. The polymer of claim 1 , comprising polymer chains formed by a polymerization catalyst system comprising {[(2,3,4,5,6-Me 5 C 6 )NCH 2 CH 2 ] 2 NH}ZrBn 2 , {[(2,3,4,5,6-Me 5 C 6 )NCH 2 CH 2 ] 2 O} ZrBn 2 , and bis(n-butyl cyclopentadienyl)zirconium dichloride.

12. The polymer of claim 1 , comprising polymer chains formed by a polymerization catalyst system comprising {[(2,3,4,5,6-Me 5 C 6 )NCH 2 CH 2 ] 2 NH}ZrBn 2 , {[(2,3,4,5,6-Me 5 C 6 )NCH 2 CH 2 ] 2 O} ZrBn 2 , and bis(n-butyl cyclopentadienyl)zirconium dichloride, in a ratio of about 3.5:2:1.

13. The polymer of claim 1 , comprising a ratio of a high molecular weight component to a low molecular weight component of between about 1:2 and 1:5.

14. The polymer of claim 1 , comprising, a high molecular weight component having a density that is between about 0.02 and about 0.05 less than a density of a low molecular weight component.

Assignees

• Univation Tech Llc

Inventors

• Wagner Juliet Bauer
• Giesbrecht Garth R
• Kao Sun-Chueh
• Jaker Stephen P

Classifications

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65916

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

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• B01J2531/0238

  Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title